3D ELECTRO, Venom and Scorpion: Full Screen
On disc 2, go to the Evolution of Spider-Man, then choose the Rogue's Gallery.
Go to Electro, at the menu button (spidey logo) press Down and you'll highlight a spidey silhouette.
Select it and you'll get the full screen version of the 3D Electro.
It works also for Venom and Scorpion.

MOVIE STILLS: COMIC BOOK
On disc one, go to Special Features then Character Files.
There will be movie credits for Tobey, Kirsten, Willem, J.K - Jonah H, Rosemary - Aunt May, and Cliff - Uncle Ben. Click on one of the pictures to see their film credits.
From there you have the option of going back to the list of those 6 actors, going forward to see more credits or back in case you missed one or something.
Each actor has 2 pages with their film credits on it.
Half on one page, the rest on the others.
The following works for everyone except for Cliff's (Uncle Ben) film credit:
On the second page of any of the remaining 5 actors, you press Up on your remote and the actor's name on top gets circled. Click on that and the info on their character comes out. From there you can see occupation, age, height, first appearance. The images shown next to the info is a comic book picture of a scene from the movie.

Todd McFarlane Interview
On disc two, go to the DVD-ROM feature and press the Up arrow and a Spidey icon will appear. Click there and you've got an exclusive interview with Todd McFarlane talking about how Spidey makes his webs.

CGI Bloopers and Gag Reel
On disc one, click on Commentaries then you will see a picture of Harry Osborn (James Franco) on the left-hand side of the screen.
If you click on the picture of Harry a new screen appears giving you access to the "CGI Bloopers & Gag Reel".

How the Webs Were Drawn
On disc 2, at the Main Menu, select Web of Spider-Man the Comic.
Click on DVD-ROM, highlight Web of Spider-Man on the DVD-ROM menu, push arrow Up, and the red face of Spider-Man appears.
Click Enter to see "A New Twist on the Webs", a documentary on how the webs were drawn.

John Romita & John Romita Jr. Feature
Insert disc two, select the Web of Spider-Man option, and then The Evolution of Spider-Man.
Once in this menu, select Artists Gallery and press the Right button.
The words "The Romitas" will appear at the upper right corner of the screen.
Select them, and check out a video feature on the Romitas (John Romita Sr. and John Romita Jr.).

History of the Sinister Six
Insert disc two and go to the comic section of the DVD, choose the Evolution of Spider-Man option, then go to Rogues Gallery.
Once you are there, at the top you will see a picture of Spidey with his spidey sense tingling.
Press Up until his spidey sense highlights, push play and you will get a page on "The Sinister Six" with information and 3D photos