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These are the issues I'm mostly pulling from for Mysterio.
Comments will contain pages and panels I'm using from other issues to inform bits of Mysterio's history, characterization, and tricks of the trade.
The Amazing Spider-Man (2014) #1.1 | "Learning to Crawl Part One: The Show Must Go On" [cameo] (29 yr)
The Amazing Spider-Man (1963) #2 | The Uncanny Threat of the Terrible Tinkerer!" [cameo, "alien" and SFX] (29 yr)
The Amazing Spider-Man (1963) #13 | "The Menace of... Mysterio!" (29-30 yr)
The Amazing Spider-Man (1964) Annual #1 | "The Sinister Six!" (29-30 yr)
The Amazing Spider-Man (1963) #24 | "Spider-Man Goes Mad!" (31-32 yr)
The Amazing Spider-Man (1964) Annual #4 | "The Web and the Flame!" (31-32 yr)
The Amazing Spider-Man (1963) #66 | To Squash a Spider 1 of 2: "The Madness of Mysterio!" (33 yr)
The Amazing Spider-Man (1963) #67 | To Squash a Spider 2 of 2: "To Squash a Spider!" (33 yr)
The Amazing Spider-Man (1963) #193 | "The Wings of the Fearsome Fly!" (35 yr)
The Amazing Spider-Man (1963) #194 | "Never Let the Black Cat Cross Your Path!" (35 yr)
The Amazing Spider-Man (1963) #195 | "Nine Lives Has the Black Cat!" (35 yr)
The Amazing Spider-Man (1963) #196 | "Requiem!" (35 yr)
The Amazing Spider-Man (1963) #197 | "The Kingpin's Midnight Massacre!" (35 yr)
The Amazing Spider-Man (1963) #198 | "Mysterio is Deadlier by the Dozen!" (35 yr)
The Amazing Spider-Man (1963) #199 | "Now You See Me! Now You Die!" (35 yr)
The Amazing Spider-Man (1963) #200 | "The Spider and the Burglar... A Sequel" [not appearing] (35 yr)
The Amazing Spider-Man (1963) #311 | "Mysteries of the Dead" (37 yr)
The Amazing Spider-Man (1963) #334 | Return of the Sinister Six 1 of 6: "Secrets, Puzzles and Little Fears..." [not appearing] (37-38 yr)
The Amazing Spider-Man (1963) #335 | Return of the Sinister Six 2 of 6: "Shocks!" (37-38 yr)
The Amazing Spider-Man (1963) #336 | Return of the Sinister Six 3 of 6: "The Wagers of Sin" [not appearing] (37-38 yr)
The Amazing Spider-Man (1963) #337 | Return of the Sinister Six 4 of 6: "Rites and Wrongs" (37-38 yr)
The Amazing Spider-Man (1963) #338 | Return of the Sinister Six 5 of 6: "Death From Above!" (37-38 yr)
The Amazing Spider-Man (1963) #339 | Return of the Sinister Six 6 of 6: "The Killing Cure!" (37-38 yr)
Spider-Man Unlimited (1993) #4 | "The Man Who Would Be Spider-Man!" (38-39 yr)
Spider-Man: Funeral for an Octopus #1 | "Spider-Man and the Scarlet Spider!" (39 yr)
Spider-Man: Funeral for an Octopus #2 | "Armed and Dangerous" (39 yr)
Spider-Man: Funeral for an Octopus #3 | "A Farewell to Arms!" (39 yr)
Comments will contain pages and panels I'm using from other issues to inform bits of Mysterio's history, characterization, and tricks of the trade.
The Amazing Spider-Man (2014) #1.1 | "Learning to Crawl Part One: The Show Must Go On" [cameo] (29 yr)
The Amazing Spider-Man (1963) #2 | The Uncanny Threat of the Terrible Tinkerer!" [cameo, "alien" and SFX] (29 yr)
The Amazing Spider-Man (1963) #13 | "The Menace of... Mysterio!" (29-30 yr)
The Amazing Spider-Man (1964) Annual #1 | "The Sinister Six!" (29-30 yr)
The Amazing Spider-Man (1963) #24 | "Spider-Man Goes Mad!" (31-32 yr)
The Amazing Spider-Man (1964) Annual #4 | "The Web and the Flame!" (31-32 yr)
The Amazing Spider-Man (1963) #66 | To Squash a Spider 1 of 2: "The Madness of Mysterio!" (33 yr)
The Amazing Spider-Man (1963) #67 | To Squash a Spider 2 of 2: "To Squash a Spider!" (33 yr)
The Amazing Spider-Man (1963) #193 | "The Wings of the Fearsome Fly!" (35 yr)
The Amazing Spider-Man (1963) #194 | "Never Let the Black Cat Cross Your Path!" (35 yr)
The Amazing Spider-Man (1963) #195 | "Nine Lives Has the Black Cat!" (35 yr)
The Amazing Spider-Man (1963) #196 | "Requiem!" (35 yr)
The Amazing Spider-Man (1963) #197 | "The Kingpin's Midnight Massacre!" (35 yr)
The Amazing Spider-Man (1963) #198 | "Mysterio is Deadlier by the Dozen!" (35 yr)
The Amazing Spider-Man (1963) #199 | "Now You See Me! Now You Die!" (35 yr)
The Amazing Spider-Man (1963) #200 | "The Spider and the Burglar... A Sequel" [not appearing] (35 yr)
The Amazing Spider-Man (1963) #311 | "Mysteries of the Dead" (37 yr)
The Amazing Spider-Man (1963) #334 | Return of the Sinister Six 1 of 6: "Secrets, Puzzles and Little Fears..." [not appearing] (37-38 yr)
The Amazing Spider-Man (1963) #335 | Return of the Sinister Six 2 of 6: "Shocks!" (37-38 yr)
The Amazing Spider-Man (1963) #336 | Return of the Sinister Six 3 of 6: "The Wagers of Sin" [not appearing] (37-38 yr)
The Amazing Spider-Man (1963) #337 | Return of the Sinister Six 4 of 6: "Rites and Wrongs" (37-38 yr)
The Amazing Spider-Man (1963) #338 | Return of the Sinister Six 5 of 6: "Death From Above!" (37-38 yr)
The Amazing Spider-Man (1963) #339 | Return of the Sinister Six 6 of 6: "The Killing Cure!" (37-38 yr)
Spider-Man Unlimited (1993) #4 | "The Man Who Would Be Spider-Man!" (38-39 yr)
Spider-Man: Funeral for an Octopus #1 | "Spider-Man and the Scarlet Spider!" (39 yr)
Spider-Man: Funeral for an Octopus #2 | "Armed and Dangerous" (39 yr)
Spider-Man: Funeral for an Octopus #3 | "A Farewell to Arms!" (39 yr)

CANON
Web of Spider-Man (2009) #4 | Gauntlet: Origins: "Mysterio" (<9 yr)
Special effects maestro Ray Bradhaus inspires a child Quentin to go into special effects as well one day. Years later, Bradhaus will become Quentin Beck's mentor and friend... and Il Mysterio will eventually inspire Mysterio's supervillain name.
Webspinners: Tales of Spider-Man #1 | As Dreams Are Made On 1 of 3: "Crash and Burn" (9 yr)
Even as a child, Quentin makes little stop-motion movies.
Symbiote Spider-Man (2019) #1 (late teens-early 20s)
Quentin Beck attends the Massachusetts Institute of Technology (MIT)!
The Spectacular Spider-Man (1976) #51 | "Aliens and Illusions" (29 yr)
Just a little more context to that one time Quentin Beck (and others) worked with the Tinkerer before becoming Mysterio.
Webspinners: Tales of Spider-Man #1 | As Dreams Are Made On 1 of 3: "Crash and Burn" (32 yr)
Two or three years after the start of Mysterio's supervillain career, Quentin Beck tries to go straight for the first time, but having a supercriminal record gets in the way.
Symbiote Spider-Man (2019) #1 (36 yr)
When a bank robbery goes wrong, someone dies -- for the very first time in Mysterio's 6-7 year career. Quentin Beck leaves without even finishing the robbery and immediately decides to quit for good. Unfortunately, Spider-Man has the wrong idea, and his attack leaves Beck feeling once again that going straight is impossible.
CHARACTERIZATION
Web of Spider-Man (2009) #4 | Gauntlet: Origins: "Mysterio" (29 yr)
Thought process under panic situations. Disconnected, scattered, panicked thoughts. Self-recriminations, too: "you idiot," "moron."
Webspinners: Tales of Spider-Man #3 | As Dreams Are Made On 3 of 3: "Wake Up Call!" (32 yr)
I just want this here. Even Spider-Man knows it.
The Spectacular Spider-Man (1976) #50-51 | "Dilemma!" and "Aliens and Illusions" (35 yr)
Again, Mysterio pretty consistently isn't out to hurt anyone.
Questprobe #2 | "Mysterio Times Two!" (36 yr)
And again.
Spider-Man (1990) #18 | Revenge of the Sinister Six 1 of 6: "Revenge of the Sinister Six" (38 yr)
This is just the funniest possible response to getting caught sneaking up, imo. No impressive act whatsoever. Just "oops."
Spider-Man (1990) #22 | Revenge of the Sinister Six 5 of 6: "The Sixth Member" (38 yr)
Mysterio being the one to step in and defuse the situation and keep Vulture and Electro from shooting each other is pretty great. Mysterio's thoughts on everyone being willing to betray everyone else, so mistrust being smart, and being constantly underestimated, is somehow even better.
The Sensational Spider-Man (1996) #1 | Media Blizzard 1 of 3: "Of Mists and Mirrors" (39 yr)
Beck wants to be appreciated pretty badly.
Spider-Man (1990) #65 | Media Blizzard 3 of 3: "Unplugged" (39 yr)
What Quentin Beck is and is not about.
TRICKS OF THE TRADE
Webspinners: Tales of Spider-Man #3 | As Dreams Are Made On 3 of 3: "Wake Up Call!" (32 yr)
A way to make a scene... notably, without actually hurting anyone.
Questprobe #2 | "Mysterio Times Two!" (36 yr)
That's some impressive special effects to be able to cook up in prison.
Questprobe #2 | "Mysterio Times Two!" (36 yr)
This is just the trolliest goddamn trick.
Spider-Man (1990) #20 | Revenge of the Sinister Six 3 of 6: "Showdown" (38 yr)
Make an enemy who wants to kill you think he's killing you while you're defeating your other enemy, and then make said other enemy look like you. Confusing but effective!
Spider-Man (1990) #23 | Revenge of the Sinister Six 6 of 6: "Confrontation" (38 yr)
Mix-up trick version 2.0, make the heroes think other heroes are the villains, make some of the heroes think some of the other heroes are dead, laugh.