Abstract Selective hydrogenation of methyl benzoate to benzyl alcohol attracts an increasing interest due to mild reaction conditions and a chlorine‐free characteristic. Cu‐Cu 2 O‐CeO 2 catalysts were fabricated by coprecipitation with controlled synthetic conditions, and the resulting catalysts exhibited a high dispersion degree even at a high Cu loading, excellent reduction properties, and a high fraction of cuprous ions versus metallic copper. The catalysts with a Cu/Ce ratio of 2:1 exhibited a methyl benzoate conversion of 93.7% as well as a selectivity to benzyl alcohol of 86.7% under applied reaction conditions. The high activity and selectivity of the Cu‐Cu 2 O‐CeO 2 catalysts may be attributed to the presence of Cu + with a relatively high fraction, and the generation of Cu + may be related to oxygen vacancies of the CeO 2 . This study may provide some insights into the development of Cu‐based heterogeneous catalyst for the selective hydrogenation of methyl benzoate to benzyl alcohol.