A domino one-pot synthesis of 2-(trifluoromethyl)benzothiazole via copper-mediated three-component cascade reaction starting from the easily accessible starting materials such as o-iodoanilines, methyl trifluoropyruvate, and elemental sulfur is reported. The present strategy displayed a comprehensive substrate scope and good functional group tolerance and enabled access to a variety of substituted 2-(trifluoromethyl)benzothiazoles. A 2-(trifluoromethyl)benzoselenazole has also been synthesized utilizing this reaction methodology.