The first example of an azidotrifluoromethoxylation of styrenes has been achieved by synergistic visible-light-mediated photoredox and silver catalysis. Trifluoromethyl arylsulfonate (TFMS) and the Zhdankin reagent were used as the trifluoromethoxylation reagent and the azide source, respectively. A good functional group tolerance and mild reaction conditions of this method are applicable to late-stage azidotrifluoromethoxylation of complex small molecules. Furthermore, the mechanistic investigations indicate the single-electron transfer involved in the reaction.