The 45-year-old singer and 35-year-old Maroon 5 frontman were announced with Tony Bennett and Lady Gaga, Jessie J and Tom Jones, and Hozier and Annie Lenox on Wednesday. Ariana Grande, Miranda Lambert and Pharrell Williams are among the other confirmed performers.
"Throughout the years, the Grammy Awards has paired musical icons with new, upcoming artists to give fans remarkable performances that can only be seen on our stage," Recording Academy CEO Neil Portnow said. "This year is no different and, once again, promises to bring together unique musical worlds in innovative ways that blend genres and create new artistic boundaries."
"Musical collaborations have become a Grammy staple, and the best part is that artists now suggest many of these duets themselves," ceremony executive producer Ken Ehrlich added. "I'm very excited about this year's special segments, and believe they'll be talked about for a long time to come."
Stefani and Levine recently coached competing teams on season seven of NBC reality series The Voice. The singer last released The Sweet Escape in 2006, while Levine debuted V with Maroon 5 in 2014. Levine will also perform the Oscar-nominated song "Lost Stars" at the 2015 Academy Awards in February.