The selective hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol (1,5-PeD) was investigated on bifunctional catalysts consisting of Pt nanoparticles (Pt NPs) and WO3/ZrO2 with loading amounts of 0.5-20 wt% WO3 (Pt/WO3/ZrO2). The relationship between structure and catalytic performance was evaluated. The loading amount of WO3 significantly affected the yields of 1,5-PeD. Pt/WO3/ZrO2 with 5 wt% WO3 loading (coverage of ZrO2 with a WO3 monolayer: ca. 50%) exhibited the highest conversion of THFA and selectivity to 1,5-PeD. The structural characterization of Pt/WO3/ZrO2 catalysts by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) revealed that tungsten oxide was loaded as two-dimensional monolayer domains at lower than 10 wt% WO3 loading and these domains covered most of the ZrO2 surface at 10 wt% WO3 loading. The W-(OH)-Zr sites at the boundaries between the tungsten oxide domains and zirconia have an important role for the selective scission of the C-O bond of THFA to produce 1,5-PeD.