During his breaks, Andrew Garfield went around New York playing basketball with kids in his Spider-Man outfit.
In this film Spider-Man uses artificial devices to shoot webs, inspired from the original comics where he possessed similar devices for his webbing (only later would he gain the superhuman ability to shoot webs). Marc Webb explained the web-shooters were a creative decision to showcase Peter's intellect: "We wanted to emphasize that these are things that Peter Parker made and that he is special himself even if he feels like he's an outsider."
Andrew Garfield requested that the song "Pure Imagination" from Willy Wonka & the Chocolate Factory (1971) be played when filming the otherwise silent scene in which Peter goes into the web harvesting room with the spiders.
Stan Lee: (at around 1h 35 mins) the headset-wearing man in the library unaware of the events going on behind him.
Tia Texada: (at around 23 mins) the woman on the subway whose black shirt is accidentally torn off by Peter, revealing her pink bra.