Demi Lovato and Teen Wolf star Tyler Posey are to host the festival special live from MTV's studios in Times Square.
Gomez and Derulo lead an all-star lineup of performers, including hip-hop stars J Cole and Mac Miller.
The Wizards of Waverly Place actress revealed the news on her Facebook page, writing: "Not sure if you know but, I will be the first performance for MTV in 2012 at the strike of midnight I will be performing at MTV's NYE Party."
MTV has invited fans to bid for seats in the audience, with all the proceeds benefiting the East Africa charity FWD.
Gomez's boyfriend Justin Bieber will also be in New York City on the night to perform alongside Lady GaGa in Times Square on ABC's Dick Clark's New Year's Rockin' Eve with Ryan Seacrest 2012.
MTV's New Year's Eve Party will air live at 11/10c on December 31.
Last week, Gomez revealed that she tries her best to smell good for Bieber at all times.
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Watch Selena Gomez and The Scene's 'A Year Without Rain' music video below: