Selective hydrogenolysis of bioglycerol to 1,3-propanedilo (1,3-PDO) is regarded as a perfect combination of a valorization of biomass-derived glycerol and an increasing demand for 1,3-propanediol. In this work, SiO2 gel was impregnated by Al(NO3)(3)center dot 9H(2)O followed by a calcination at a high temperature, and a strong interaction between SiO2 and Al2O3 led to a homogeneous dispersion of the Al2O3 on the surface of the substrate SiO2. The Al2O3-decorated SiO2 was used to load WOx and Pt sequentially and the resulting Pt-WOx/SiO2-Al2O3 catalysts were found a markedly enhanced surface acidity due to a strong interaction between the Al2O3-modified support and the WOx domain as well as the introduced ion exchange functionality by Al2O3 addition. A well-defined matching between the acidic and metallic sites was realized by turning the content of the Al2O3, and the glycerol conversion and 1,3-PDO selectivity were enhanced by a large margin on the optimized Pt-WOx/SiO2-Al2O3 catalyst. Graphic A markedly improved reactivity in bioglycerol hydrogenolysis was realized using the Pt-WOx catalysts supported over Al2O3-modified SiO2.