Enantioselective catalytic Giese addition of photogenerated α-alkoxy radicals to acyl pyrazolidinones can be accomplished using a tandem Sc(III) Lewis acid/photoredox catalyst system. Surprisingly, the excited-state oxidation potential was not the only important variable, and the optimal photocatalyst was not the strongest oxidant screened. Our results show that both the oxidation and reduction potentials of the photocatalyst can be important for the reaction outcome, highlighting the importance of holistic considerations in designing photochemical reactions.