The CeC bond and CeO bond cleavages in glycerol hydrogenolysis were compared over Pt and Ru supported on ZrO2 and WO3/ZrO2 (ZrW). The prepared catalysts were characterized by nitrogen adsorption/desorption, X-ray powder diffraction, transmission electron microscopy, CO and H-2 chemisorption, O-2 titration, H-2-temperature programmed reduction, diffuse reflectance infrared Fourier transform spectra of adsorbed CO and Fourier transform infrared spectra of pyridine adsorption. The electron density of metal on ZrO2 was different from that on ZrW, resulting in the different ability on CeC bond cleavage in glycerol hydrogenolysis. Pt/ZrW exhibited a better hydrogen activation and spillover capacity than Ru/ZrW, leading to a higher selectivity of 1,3-propanediol. The effect of H-2 pressure was also studied and reaction routes of glycerol hydrogenolysis to propanediols were discussed.