The USO concert also will feature Sugarland, Grace Potter, and Ann and Nancy Wilson, VH1 said Saturday.
The show, with Kathy Griffin as host, will be televised on VH1, and internationally on the Armed Forces Network.
Perry, Keri Hilson and Jennifer Nettle open the show, paying homage to the troops with the classic Army song "Boogie Woogie Bugle Boy."
First lady Michelle Obama, singer Brandy, model Marisa Miller, and Nicole "Snooki" Polizzi and Mike "The Situation" Sorrentino from MTV's "Jersey Shore" will also appear on the program.
Footage for the show was filmed at military bases around the world, including a stop in Kuwait.
Obama will speak about the work of the USO.