Herein,unprecedented rhenium-catalyzed decarboxylative oxytri-/difluoromethylation and Heck-type trifluoromethylation of styrenes have been developed by using hypervalent iodine(Ⅲ) reagents derived from cheap,stable,and easy-handling fluorinated carboxylic acids.Mechanistic studies revealed a radical decarboxylative trifluoromethylation pathway occurring in these reactions.