Instructions
Run around New York City and select the story missions you come across in order to encounter into villains. During the story missions you will run into every available villain from the New Goblin to Sandman. You will be able to snap pictures of them when you see them. However, only Peter Parker can take pictures of villains, not Spiderman. You can't take pictures while performing other moves either. The best time to take pictures of villains is during the Daily Bugle missions.
Pull out your camera when you come across a villain. You can use your camera before or during a fight. You may also run across a villain randomly without them knowing you are there and snap a picture of them. If you take a picture during a fight be sure to back up and avoid damage since Peter is not as strong as Spiderman.
Press the action button on your controller to take the picture. The action button on the Xbox 360 is the "A" button. On the PlayStation 2 and PlayStation Portable the action button is the "X" button, and on the Wii the action button is the "A" button. If you're playing on the PC you set your own action button in the "Setting" menu.
Complete the Master Tourist photo achievement, only available in the Xbox 360 version, by taking a photo worth 500 points or more. You can get this from the Daily Bugle mission at the Arsenic Candy Beauty Show. Stand back and take a picture of the villains as they all come at you at once. Get as many villains in the frame as possible by zooming up with the left analog stick and press the "A" button quickly to avoid taking damage. The achievement will pop up on the screen when you earn it.