The pilot will be based around Kryptonian Kara Zor-El (Melissa Benoist) embracing her superpowers after hiding most of her life, reported Entertainment Weekly.
Harewood will be playing DC Comics character Hank Henshaw, a former CIA agent who is put in charge of the US government's Department of Extra-Normal Operations.
Leigh has been cast as Kara's science-obsessed foster sister Alexandra 'Alex' Dancer.
'Supergirl' will also feature Laura Benanti, Calista Flockhart and Mehcad Brooks playing iconic DC Comics characters Alura Zor-El, Cat Grant and Jimmy Olsen.
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