A novel and efficient 1,2-oxidative trifluoromethylation of olefins employing Ag(O2CCF2SO2F) as a trifluoromethyl source is described with O2 as the oxidant, which provides access to a variety of valuable α-trifluoromethyl-substituted ketones. The broad substrate scope, feasibility of large-scale operation, and derivatization reactions of α-trifluoromethyl ketones demonstrate the promising utility of this protocol.