Our results on benzylic photooxidation and oxidative cyanation mediated by Sc(OTf)3 as sole photocatalyst break the long-held belief that Sc 3+ salts serves only as a potent Lewis acids for activating organophotocatalysts or substrates. We expect that Sc 3+ salts can find applications as photocatalysts also in other oxidative organic reactions, some of which are now under investigation in our laboratory. From a general perspective, our examples could pave the way for the exploration of other redox-innocent metals in photoredox catalysis. was monitored by 1 H NMR. When the reaction was completed, the solvent was evaporated, and the crude product was purified either by column chromatography on silica gel or by extraction (see Supplementary Section S2 for details). General procedure for photocatalytic oxidative cyanation of arenes Small scale experiments (C). A vial was charged with a mixture of the substrate (140 μmol), Sc(OTf)3 (5 mol%, 7 µmol) and TMSCN (12 equiv., 1.68 mmol) in MeCN (250 μL). The reaction mixture was bubbled with oxygen (2 min) and then stirred at 45 °C under irradiation with 400 nm LEDs. After selected time, the reaction mixture was diluted with DMSO-d6 and the yield was determined by 1 H NMR.