Efficient redox reactions of benzyl-type radicals were achieved by irradiating an aromatic donor/acceptor pair with substituted dibenzyl ketones as a radical precursor in MeOH-MeCN. In this system, the aromatic radical ion pair was generated by photoinduced electron transfer followed by one-electron oxidation and reduction of photogenerated benzyl radicals (R .) by the radical ions to afford benzyl cations (R(+)) and anions (R(-)). The cations and anions were trapped by MeOH to yield ROMe and RH, respectively. The relative product ratios were determined for a variety of donor-acceptor pairs, reflecting the relative efficiencies of the redox reaction of benzyl radicals with a steady-state concentration of radical ions. The selective formation of carbocations or carbanions was achieved in some sets of donor/acceptor pairs. Assuming that the radical ions exist in a 1:1 ratio in the steady state, the product ratios are equal to the relative electron transfer rates, which are analyzed in terms of the free energy changes of the processes. The present results indicated that the rates became maximal at the energy gap of ca. -0.5 eV, representing a novel example of the Marcus inverted region. This interpretation is discussed in comparison with other related cases and in relation to recent theories on electron transfer rates.