Herein, we describe a nickel-catalyzed hydrotrifluoroalkylation of terminal alkyne for the synthesis of a manifold allylic trifluoromethyl terminal alkene. The combination of nitrogen and phosphine ligands, especially electron-rich ones, plays an indispensable role in the course of the reaction, promoting the reactivity to a remarkable level, demonstrating high efficiency, broad substrate scope, and favorable functional group compatibility. The strategy provides a facile method for the synthesis of diversified allylic CF3-containing drugs and bioactive molecules.