We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C–H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl–OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H₂O or CH₃CN cosolvent is presented.