In this work, CuO/ZnO/Al2O3 catalysts were prepared by adjusting the initial alkali concentration in the process of co-precipitation. The correlation between the structure and catalytic activity was studied, and the catalyst derived from LDHs (layered double hydroxides) structure exhibited the highest activity in the hydrogenation of fatty esters as well as high selectivity to fatty alcohol, producing fatty alcohol with a yield above 98%. The high catalytic performance was attributed to relatively high dispersion (small crystal size) and the high reducibility of copper species. In addition, the active species was discussed and the Cu+/Cu-0 were supposed to be the active site for the present hydrogenation. (c) 2012 Elsevier B.V. All rights reserved.