Twenty (20) Villain First Appearances Worth a Fortune
When collectors talk about valuable first appearances, the focus often falls on superheroes—think Superman in Action Comics #1, Batman in Detective Comics #27, or Spider-Man in Amazing Fantasy #15. But let’s not forget: Being bad, really bad, can also spark collector interest—and serious price tags.
This list highlights twenty villain first appearances that are worth a small fortune. For consistency, all prices are based on the value of copies in CGC Fine (6.0) condition. Lower-grade copies go for less, and higher grades for more.
We’re starting off cold—very cold—with the first appearance of Mr. Freeze, then known as Mr. Zero. This early Silver Age issue has just over 1,000 copies on the CGC census and commands about $3,600 in 6.0. Freeze looked quite different here compared to his later versions, but his craving for Batsicles remains consistent through the decades.
At #19 is one of Spider-Man’s most iconic foes: Doc Ock. This issue features a great silhouette of the villain and a striking green outline on the speech balloon. With over 3,400 CGC-census copies, a Fine copy will cost you around $3,700.
Thor’s archenemy Loki makes his debut just two issues after the God of Thunder himself. Jack Kirby’s cover is a masterclass in visual storytelling—Loki looms at the top, looking down on everyone as if to say, “I’m better than you… even you, Thor!”
The first appearance of the Vulture, with his eery old-man-vulture face, comes in at #17. The red-green contrast on the cover is especially eye-catching.
Quick shoutout to Amazing Spider-Man #1–20: an unbelievable stretch introducing villains like Sandman (#4), Lizard (#6), Electro (#9), Mysterio (#13), Green Goblin (#14), Kraven (#15), and Scorpion (#20). While they didn’t make the list based on price, they’ve all left a lasting mark.
Usually, a thirst for knowledge is a virtue. But Brainiac takes it too far—shrinking cities and destroying their home planets in the process. This 1958 book has only about 700 CGC-census copies, making it quite rare and valued.
The Rock’s alter ego debuts in this Golden Age gem. A Fine copy will run about $6,500. Why is this worth more than Action #242? Scarcity. Marvel Family #1 has only about a quarter of the census copies of Brainiac’s debut.
Cheetah—an early nemesis of Wonder Woman—takes the 14th spot. Thankfully, she appears right on the cover, adding even more appeal to this Golden Age issue.
Tied at #12 is the most modern villain here—Shredder—who debuts alongside the Ninja Turtles in this independently published Mirage Studios book. Its low print run makes it scarcer than many Silver Age keys. (And yes, we’ll come back to the Shredder controversy shortly…)
Hiding behind a wholesome baseball-themed cover is one of DC’s darkest villains: the Scarecrow. This early Golden Age issue also goes for around $8,000 in Fine.
Talk about taking the air out of the room—Doctor Doom debuts here, quite literally turning down the oxygen to snuff out the Fantastic Four. This is the first book on the list to crack the $10,000 mark
Two-Face, the coin-flipping, dual-personality villain, makes his debut here. A timeless Batman foe with a memorable origin.
The most abundant book on this list (almost 7,000 on the census), yet still fetching $13,500 in 6.0. That’s the power of Magneto… and, yes, also the X-Men. The demand is undoubtedly driven by the debut of the entire team, but Magneto’s role can’t be dismissed. If his first appearance were in, say, X-Men #5, it might still land on this list—unlike Shredder, whose value might not stand on its own.
Riddle me this: what Batman villain’s debut can cost you $14,000 in Fine? The Riddler. A 9.6 once sold for $456,000 in 2021, showing how dramatically grade and a hot market can affect price.
Also priced around $14,000, this issue features the first appearance of the Penguin. Sadly, he doesn’t appear on the cover—but the tuxedoed villain made frequent cover appearances in subsequent issues.
The rarest and earliest book on this list, with only 28 CGC-census copies. The Claw debuts here, predating even the hero who would become his primary nemesis, Daredevil (Golden Age), who wouldn’t arrive until five issues later.
The second-rarest book on the list, this is one of the most iconic villain-first-appearance covers ever. Grundy emerges onto the scene as a powerful Green Lantern foe.
The origin of the Joker—featuring Red Hood—ranks high for its importance and value. That makes six Batman villains so far in the top 20. Batman has the deepest, and on average, most expensive rogue gallery. Spider-Man may match him in quality, but his villains’ first appearances are easier to find and cost less.
Gene Hackman would be proud. Luthor may lack superpowers, but his intellect and villainy more than make up for this shortcoming. He doesn’t appear on the cover of Action Comics #23, but the old school Superman image pleases the eye nonetheless. A Fine copy costs about as much as a new car.
The most valuable first appearance of a Marvel villain, Red Skull’s debut coincides with Captain America’s, driving the price north of $200,000. Even Cap #3, with Skull’s first cover appearance, goes for around $40,000—still enough for second place.
The villain of all villains. Joker makes his first appearance not on the cover, but inside—on page three. Still, this Golden Age key tops the list at around $400,000 in Fine condition. Want a copy? You might have to choose between it and a house.
Final Thoughts
Here’s to the villains—the monsters, madmen, and masterminds who push our heroes to be their best. Whether they’re frozen, clawed, two-faced, or just plain evil, their first appearances remain among the most valuable in the hobby.
