Sam Raimi's Spider-Man 4 was never to be, but apparently we would've seen at least one key character from Spider-Man comics make her live-action debut in the movie, that being Black Cat AKA Felicia Hardy.
The character would've been played by Anne Hathaway, who revealed her casting on the Happy Sad Confused Podcast. "If [Spider-Man 4] had gotten made, I don't know if I would've been considered for [The Dark Knight Rises]," she said. "Perhaps [Christopher Nolan] would've said, 'No, she's occupied in another universe.'"
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Hathway did get to prove herself as a feline femme fatale in 2012's The Dark Knight Rises, but it would've been interesting to see her as Marvel's Black Cat. Perhaps soon we could see a live-action version of Peter Parker's other love interest.