Hydroxylapatite (HAP), SBA-15, and MCM-41 supported copper catalysts were used for the coupling reaction between ethanol dehydrogenation and maleic anhydride hydrogenation. CuO species were completely reduced to metallic copper (Cu0), which was the active site for the coupling reaction. Cu/SBA-15 and Cu/MCM-41 catalysts favored the formation of acetaldehyde and diethyl succinate. Cu/HAP catalysts with high basicity and small crystallite-sized Cu0 nanoparticles favored the dehydrogenation of ethanol to ethyl acetate with the maximum selectivity of 69.5% and the hydrogenation of maleic anhydride to γ-butyrolactone with the maximum selectivity of 89.6%. The coupling reaction had good compensation for reaction heat and hydrogen.