Diehard fans of the Spider-Man comics would certainly be able to remember the first time he faced off against Mysterio and Doctor Octopus.
Spider-Man has arguably the most recognizable villains' rogues gallery in Marvel Comics. What might come as a surprise is that most of these villains debuted in the first year of Spider-Man comics and were so great that they all survived the tests of time and became icons themselves.
As a teenage crimefighter, Spider-Man mostly fought street-level villains, and that might be what helped them with their longevity in Marvel Comics, some of the villains even going on to star in other hero's comic books. While a couple of his greatest villains, such as Green Goblin, appeared in his second year, the first 1o Spider-Man villains remain memorable.
Spider-Man's first appearance was in Amazing Fantasy #15. However, the villain in that comic was a thief and killer and not a true supervillain. It wasn't until Amazing Spider-Man #1 (by Stan Lee and Steve Ditko) that Spider-Man battled a true villain.
The first supervillain was The Chameleon, who disguised himself as Spider-Man and made the hero look like a villain. This was hugely important as Chameleon was part of why no one trusted Spider-Man for years into his career.
In Amazing Spider-Man #2, Spider-Man went up against his first villain with superpowers as he battled The Vulture. This was Adrian Toomes, who had wings he created as a brilliant scientist.
This didn't show his origin story and what caused him to become a villain. Instead, Vulture was introduced as a common thief, who used his wings and powers to commit his crimes. Spider-Man also battled a secondary villain in this issue known as The Tinkerer.
One of Spider-Man's greatest enemies showed up in Amazing Spider-Man #3, as Doctor Octopus was introduced. This put the very smart teenage Peter Parker up against the brilliant Otto Octavius for the first time.
It also showed Doc Ock's origin story as he was caught in an explosion, which saw his mechanical arms fused to his body and his descent into madness. He eventually tries to take over a nuclear power plant before Spider-Man stops him.
Sandman shows up for the first time in Amazing Spider-Man #4. Sandman attacks Spider-Man first in this issue before his origin is revealed as a thief, who was caught in a radioactive testing area and turned into a sand-like creature.
When Sandman shows up at Spider-Man's high school, a battle breaks out, and the two end up in a massive fight. Spider-Man then has to use his brains to figure out how to stop the slippery villain.
Amazing Spider-Man #5 is the only time in the first 10 issues that Spider-Man fights a villain from another superhero comic book. This battle put Spider-Man up against the Fantastic Four's arch-nemesis, Doctor Doom.
In this issue, Doom thinks Spider-Man is really a villain (based on the newspaper reports) and asks to team with him. However, they ended up battling instead. This was the first time Spider-Man didn't capture the villain, as Doctor Doom escaped.
In Amazing Spider-Man #6, Spider-Man battled his first sympathetic villain. A monstrous creature known as The Lizard is rampaging in Florida, and J. Jonah Jameson challenges Spider-Man to stop him.
Spider-Man goes to Florida to stop The Lizard. However, when he arrives, he finds himself in a bit of a moral dilemma once he discovers why Curt Connors had transformed into the creature in the first place. Instead, Spider-Man decides to save Curt Connors rather than send him to prison. Connors eventually became a quasi-ally for Spider-Man.
The least notable of Spider-Man's first 10 villains he ever fought in comics was the being known as The Living Brain. He showed up in Amazing Spider-Man #8 (Spidey fought Vulture again in the previous issue), and this was a science project turned bad.
The Living Brain was a computer that could answer any question if given the correct input. When two men try to steal it, it short-circuits and comes to life, going on a rampage. The scientist who created it would bring it back years later.
In Amazing Spider-Man #9, the Wall-Crawler battled Elektro for the first time. In this first introduction to the villain, Elektro was a common thief who used his electricity powers to rob an armored truck and other heists.
When J. Jonah Jameson prints a story that claims Elektro is Spider-Man, it forces the Wall-Crawler to leave his ill Aunt May to try to stop and bring the new villain down.
The next villains Spider-Man fought was a group, and while they never reached the level of the upcoming Sinister Six, the Enforcers were still memorable.
This gang included the leader, Big Man, and his minions, Montana, Fancy Dan, and Ox. It was a fun story and one that played out in later animated series, and proved that the Sinister Six would be a perfect antagonist in the future.
The 10th supervillain that Spider-Man ever fought came in Amazing Spider-Man #13. Spider-Man had just spent the last two issues involved in his first multi-issue story arc against Doctor Octopus, and now he had to fight someone who could warp reality.
This was Mysterio, who actually made his first appearance behind the scenes in Amazing Spider-Man #2. Here, Mysterio pulled the same stunt that Chamelon did, pretending to be Spider-Man and robbing several businesses. Spider-Man had to prove his innocence by beating the new villain.