An organic photoredox-catalyzed dehydroxylative trifluoromethylation of allylic alcohols was developed in an environmentally benign manner. In this reaction, the readily available CF3SO2Na was selected as the trifluoromethylation reagent. The in situ generated byproduct SO2 was reutilized to activate C-OH bond, which enabled this dehydroxylative trifluoromethylation to be performed conveniently. A variety of multifunctionalized CF3-allylic compounds were obtained in high yields and excellent stereoselectivity.