Abstract A series of Cu‐WO x ‐TiO 2 catalysts for heterogeneous catalysis with different molar ratios of copper and tungsten species loadings were prepared by modified evaporation‐induced self‐assembly method. Their physical and chemical properties were characterized by X‐ray diffraction, liquid N 2 sorption, Py‐IR, Raman, inductive coupled plasma, X‐ray photoelectron spectroscopy, scanning electron microscope‐energy dispersive X‐ray spectroscopy and transmission electron microscope techniques, and their catalytic performances were investigated in the hydrogenolysis of glycerol. The mesoporous framework for Cu‐WO x ‐TiO 2 materials can be kept well when the molar ratio of tungsten species is lower than 6%. Although the tungsten species loading is the same, the 2Cu‐6WO x ‐ TiO 2 sample has distinctly more Brønsted acid sites than the 2Cu‐6WO x /TiO 2 ‐I sample prepared by impregnation method, which is owing to homogeneous tetrahedrally WO x species dispersion resulting in the formation of W 5+ species. The 2Cu‐6WO x ‐TiO 2 sample has a higher catalytic performance than other samples, and the glycerol conversion of 12.7%, 1, 3‐Propanediol selectivity of 32.3% and the ratio of 1, 3‐Propanediol to 1, 2‐Propanediol of 1.17 can be obtained. The 2Cu‐6WO x ‐TiO 2 sample shows good catalytic reusability, whose glycerol conversion 12.1% and 1, 3‐PDO selectivity 30.8% can be reached even though after repeated reaction for 5 times.