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X-Men #101 CGC 9.8 (W) Origin & 1st appearance of Phoenix
Copper Age
Amazing Spider-Man #41 CGC 6.5 (OW-W) 1st Rhino Appearance
Silver Age
X-Men #4 CGC 6.0 (OW) 1st appearance of Quicksilver, Scarlet Witch, Toad
Silver Age
Amazing Spider-Man #46 CGC 8.0 (OW-W) 1st Shocker Appearance
Silver Age
Batman Adventures #12 CGC 7.5 (W) 1st Appearance of Harley Quinn
Modern Age
Amazing Spider-Man #18 CGC 4.0 (OW-W) 1st Ned Leeds Appearance
Silver Age