Reductive cleavage of pars-substituted benzyl chlorides 4-Y-C6H4CH2Cl (Y = NH2, MeO, Me, H, F, Cl, CF3, NO2) (1) and of C6F5CH2Cl (2) has been studied by MP2 and DFT methods. In contrast to the MP2 calculations, DFT calculations reveal the formation of radical anions from benzyl chlorides including those bearing donor substituents, The calculations also show the possibility of the formation of complexes of benzyl radicals with the chloride anion along the path of the reductive cleavage.