Inexpensive Ni–Sn-based alloy catalysts, both bulk and supported, exhibited high selectivity in the hydrogenation of a wide range of unsaturated carbonyl compounds and produced unsaturated alcohols almost exclusively. For the bulk Ni–Sn alloy catalysts, a relatively high reaction temperature of 453 K was required to achieve an efficient hydrogenation of CQO rather than CQC. The catalyst that consisted of the Ni–Sn alloy dispersed on TiO2 allowed a remarkable reduction of the reaction temperature to 383 K. Both the Ni3Sn2 and Ni3Sn alloy phases were found to be responsible for the enhancement of the chemoselectivity. The Ni–Sn alloy catalysts were reusable without any significant loss of selectivity