The actress and the singer, who performed together on Saturday Night Live last month, will also be calling on some famous friends for help: the Jim Henson Company Puppets, PEOPLE has learned.
It's not yet known what song they'll perform, but what's clear is the bond that Paltrow and Cee Lo formed when recording a new version of his Grammy-nominated hit "F--- You."
Cee Lo says Paltrow expressed "really feeling and appreciating what I had done artistically. That was awesome to come from her and feel her energy."
Paltrow first performed a toned down version of the song on Glee.
The 53rd Annual Grammy Awards will air on Feb. 13 at 8 p.m ET/PT on CBS.