Netflix confirmed Friday that Theron, 45, and Washington, 44, will star in its forthcoming adaptation of the Soma Chainani fantasy young adult novel.
Theron will play Lady Lesso, while Washington will portray Professor Dovey. The pair join previously announced stars Sofia Wylie and Sophia Anne Caruso.
The new film is adapted by David Magee and Laura Solon and directed by Paul Feig. Chainani, Zack Roth and Patricia Riggen serve as executive producers.
The School for Good and Evil centers on Sophie and Agatha, two best friends who attend the titular School for Good and Evil, a place where students are trained to be fairy tale heroes and villains. To their surprise, Sophie is placed in the School for Evil, while Agatha is put into the School for Good.
"I know what school I'm applying to! So thrilled to welcome Charlize Theron and Kerry Washington to the School for Good and Evil! Everyone, prepare to get schooled!" Feig tweeted Friday.
The School for Good and Evil is the first novel in Chainani's six-book series. The final book, One True King, was released in June.
Theron most recently starred in the Netflix film The Old Guard, while Washington appeared in the Netflix movie The Prom.