We developed an efficient way to prepare benzyl 3-phenylpropiolates via copper-catalyzed coupling between corresponding benzyl halides and alkynoic acids under ligand-free condition. This methodology is also suitable for aromatic and alpha,beta-unsaturated acids. The desired esters could be obtained in good yields. We developed an efficient way to prepare benzyl 3-phenylpropiolates via copper-catalyzed coupling between corresponding benzyl halides and alkynoic acids under ligand-free condition. This methodology is also suitable for aromatic and cinnamic acids. The desired esters could be obtained in good yields.