Giamatti will star opposite Andrew Garfield, Emma Stone, Jamie Foxx, Shailene Woodley, Sally Field, Martin Sheen and Dane DeHaan, which is due to enter production next month.
Felicity Jones (Like Crazy), who recently debunked rumours that she was in line for the female lead in Captain America: The Winter Soldier, is also said to be in talks with Sony for an undisclosed role.
The Amazing-Spider Man 2, which will once more be directed by Marc Webb, boasts a script by returnees Alex Kurtzman and James Vanderbilt, along with newcomers to the series Roberto Orci and Jeff Pinkner.
Not much is known about the plot of the sequel at this point, other than the fact it’ll feature appearances from another Spidey villian Electro (Foxx), Mary-Jane Watson (Woodley) and Harry Osborn (DeHaan).
The Amazing Spider-Man 2 will be released in the UK on April 18, 2014.