The Tiffany Network will broadcast the show from Nokia Theatre at LA Live later this month to benefit a variety of non-profit organisations.
Dierks Bentley and Josh Groban have also signed on to perform on Teachers Rock, which honour educators from across the US who have contributed to their communities.
Teachers Rock will feature taped vignettes where stars including Usher, Meryl Streep, Dave Grohl, Adam Levine and Jennifer Garner sharing memories of their favourite teachers.
Maggie Gyllenhaal and Viola Davis - who appear in the new education-themed movie Won't Back Down - will take part in the telecast as well.
Teachers Rock, co-sponsored by Walmart, airs Friday, August 17 at 8/7c on CBS.
Watch a trailer for Won't Back Down below: