The special is set to air Dec. 3.
Blige will play Evillene, the Wicked Witch of the West, while Queen Latifah will star as the Wiz, "the mysterious and powerful wizard who holds the keys to the Emerald City, but whose metamorphosis from ordinary to extraordinary is itself a hoax," press notes reveal.
The project reunites Queen Latifah with producers Craig Zadan and Neil Meron. The trio previously collaborated on the movie musicals Chicago and Hairspray, as well as the small-screen adaptation of Steel Magnolias.
"We are so happy reuniting with Latifah," Zadan and Meron said in a joint statement. "We've been friends for a long time and we've had quite a lot of success together. To see her play the iconic role of the Wiz and make it her own is going to be one of the joys of producing this event."
"I can't wait to watch Mary bring the badness that is Evillene," added director Kenny Leon. "Her talent range is off the charts and I know audiences won't be able to take their eyes off her."
Stephanie Mills was previously announced to portray Auntie Em in The Wiz Live! Mills is best known to many for playing Dorothy in the original Broadway production of The Wiz.
Additional casting news will be announced in the coming weeks, NBC said.