The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radi-cal precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AIEgen as well as estrogen receptor-β agonist(R)-diarylpropionitrile(DPN).