Tunable reaction selectivity on a single catalyst is a continual goal in chemical syntheses. Herein, we report an unexpected light-directed intermediate selectivity using well-known plasmonic photocatalysts. We observed distinct intermediate selectivity behaviors between using UV and visible light irradiations. Chemical computations and quenching experiments suggest that the radicals generated by the plasmonic excitation govern the light-directed selectivity. The broader impact of this work ranges from selective yield of desirable intermediates for subsequent syntheses without tedious separation procedures, to arousing interest in examining new opportunities for plasmonic photocatalysts.