Display omitted •WOx species existed as monotungstate, polytungstate and crystalline m-WO3 phase.•Addition of WOx to Pt/Al2O3 induced hydrogen spillover.•42.4% 1,3-propanediol yield was achieved over Pt–10WOx/Al2O3.•1,3-Propanediol yield was proportional to the concentration of Brønsted acid sites.•1,2-Propanediol yield was proportional to the concentration of Lewis acid sites. Despite 1,3-propanediol possessing high economic value, its production from glycerol hydrogenolysis is a challenging task. Herein, a series of WOx promoted Pt/Al2O3 catalysts with various WOx contents were prepared and investigated for selective production 1,3-propanediol from glycerol hydrogenolysis. To explore the structure feature, these catalysts were fully characterized by BET, CO chemisorption, HRTEM, XRD (in situ XRD), Raman, NH3–TPD, Py–IR, H2–TPR, and XPS. Among them, Pt–10WOx/Al2O3 achieved the highest 1,3-propanediol yield up to 42.4%, which was ascribed to the large concentration of Brønsted acid sites, strong electronic interaction between Pt with WOx and hydrogen spillover. The strong correlation between 1,3-propanediol yield and Brønsted acid site indicated its essential role for the formation of 1,3-propanediol. Meanwhile the linear correlation between 1,2-propanediol yield and Lewis acid site gave direct evidence that Lewis acid site preferentially generated 1,2-propanediol.