A visible-light-induced trifluoromethylsulfonylation reaction of diazo compounds is herein reported. This developed synthetic method captures the relatively rare trifluoromethyl sulfone radicals via coordination to the Mn(acac)3 catalyst, delivering the corresponding α-trifluoromethyl sulfone esters in good to moderate yields (up to 82%). This protocol exhibits broad substrate scope and is easily carried out under mild reaction conditions. Furthermore, a plausible mechanism of the reaction was investigated through DFT calculations.