A new method has been developed for the Cu-catalyzed C–H trifluoromethylation of 3-arylprop-1-ynes for the selective construction of allenic Csp2–CF3 and propargyl Csp3–CF3 bonds. The selective formation of allenic Csp2–CF3 and propargyl Csp3–CF3 bonds can be controlled by modifying the reaction conditions.