Site-selective and late-stage C-H trifluoromethylation (including pentafluoroethylation) of arylthianthrenium salts using in situ generated CuCF3 from Ruppert-Prakash reagent under visible light was found to be significantly accelerated by a catalytic amount of rac-BINAP, allowing the reaction to complete within 15 min under very mild conditions without using any additional photoredox catalysts. The process showed a broad substrate scope, high efficiency, and excellent regioselectivity, which holds the promise to accelerate the discovery of fluorinated medicinal compounds.