The enantioselective cyanoalkylation of styrenes by a cooperative photoredox and copper catalysis system has been established, providing straightforward access to structurally diverse enantioenriched alkyl nitriles in good yields with excellent enantioselectivities under mild conditions via deoxygenation of alkoxyl radicals with organophosphorus compounds(III). In addition, the reaction features a wide substrate scope and good functional group tolerance, and the resultant alkyl nitriles could be easily converted into a series of chiral carboxylic acids, amides, esters, etc.