For the first time, intermolecular iodotrifluoromethoxylation between alkenes and NIS with AgF as the catalyst and TFMS as the trifluoromethoxylation reagent has been explored. The practical processes, good functional group tolerance, and easy scalability make this reaction an attractive protocol for the synthesis of trifluoromethoxylated iodides, which can be readily used for further synthetic manipulation.