One of the more interesting aspects of the Silver Age of Comics was the increasing use of fashionable headgear, oddly enough just as the men's hat business was collapsing. I don't know if some haberdashers, driven to despair by their shrinking market, went into designing chapeaus for supervillains or what, but it is undeniable that especially in Marvel Comics, toppers became very elegant during the 1960s.
In Spiderman comics, Mysterio went in for the opaque fishbowl look:
The Green Goblin preferred a stocking cap:
The Whirlwind (fka the Human Top) went in for the knight's helmet:
Magneto's was more football-looking:
Daredevil baddie the Gladiator went for a stylish, yet simple look:
While his occasional partner in crime the Masked Marauder had a weird combination of miner's helmet, goggles and a veil:
One of the wildest hats resulted in a famous nickname: Ol' Hockey-Stick Head:
At least Galactus confined himself to one style; Odin was the Imelda Marcos of hood ornaments:
Update: Commenter Ralph C noted one particular face covering that never came off: Baron Zemo from the early Avengers: