A method for radical addition to alkenes is reported which is based on the photosensitized oxidation of a tetraalkylstannane by an excited acceptor (A*), fragmentation of the radical cation, and addition of the thus formed radical to an electron-withdrawing substituted alkene (acrylonitrile and dimethyl maleate). Aromatic nitriles and esters can be used as the electron accepters, and they are chosen in such a way that their radical anion (A(.-)) reduces the adduct (and not the educt) radical. In this way the adduct radical is reduced and protonated to yield the end product, and the acceptor functions as a nonconsumed electron transfer sensitizer. In several cases the alkylation occurs more efficiently in the presence of a secondary donor (phenanthrene or biphenyl). However, when the acceptor is too easily reduced in the ground state (as with 1,2,4,5-benzenetetracarbonitrile), coupling of the adduct radical with A(.-) competes with its reduction.