Sam Raimi's Spider-Man movies made it three movies in before the series was scrapped and rebooted as the Amazing Spider-Man. Tobey Maguire was replaced by Andrew Garfield as Peter Parker/Spider-Man and our story began all over again (kind of like it's about to with Spider-Man: Homecoming).
While the fourth installment in the Raimi series never saw the light of day, illustrator and writer Jeffrey Henderson has revealed a few of the storyboards for the film that never was. Interestingly enough, Mysterio (below) and Vulture (above) would have been the villains.
It should be noted that the Vulture will be in the upcoming Spider-Man movie starring Tom Holland.
According to Henderson, the fourth installment was going to knock our socks off:
It would’ve been one absolutely kick ass movie. Seriously. We were working on some crazy- cool stuff, because everyone, from top to bottom, felt that Spidey 3 was a bit of a 'missed opportunity’, and we all really wanted to help Sam take SM4 to another level so he could end the series on a high note.
Within the slides there's a picture of someone that looks terribly like Angelina Jolie, if she had been included in the film it's likely that she would have been Black Cat or Silver Sable, but that's something we won't know because this movie never happened.
You can check out the rest of the storyboard here.