A trifluoromethylalkynylation reaction of gem-difluoroalkenes with alkynyl sulfoxide by photoredox radical addition with good functional group tolerance in moderate to high yields, is developed for the synthesis of α-trifluoromethyl alkyne. This reaction features simple operation and inexpensive raw materials and provides an expeditious route to synthesize biologically relevant fluorine-containing alkynyl compounds with diverse structural skeletons.