You know that with the announcement of the Black Knight as part of the upcoming Eternal movie that this comic was bound to make our list. Technically there are two comics that qualify as Dane Whiteman’s first appearance – however we want to note that it is Avengers #48 wherein he first wore the iconic costume as the Black Knight!
As this is a silver age comic, Hicollector recommends you buy this issue at 7.5 or higher.