A novel trifluoromethylation of (hetero)arenes and polarized alkenes using simple trifluoroacetic anhydride (TFAA) as the low price CF 3 source under photoredox catalysis was developed without using additives such as bases, hyperstoichiometric oxidant, or auxiliaries. The reaction showed excellent tolerance, including to some important natural products and prodrugs, even on the gram scale and extended to ketones. This simple protocol provides a practical utilization of TFAA. Several perfluoroalkylations and trifluoromethylation/cyclizations were successfully achieved under identical conditions.