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Vapor phase catalytic transfer hydrogenation of aqueous levulinic acid (LA) with formic acid (FA) as a hydrogen source was carried out over copper loaded on to several SiO2supports having different physicochemical properties. The SiO2supports and Cu–SiO2catalysts with different support properties were characterized by XRD, TPR, XPS, NH3-TPD and UV-vis techniques to evaluate the copper species and its interaction with the support. The SiO2support alone showed lower LA conversion and low selectivity to GVL whereas Cu–SiO2catalysts were found to show high conversion and selectivity to the desired product with formic acid as the hydrogen source. The difference in the activities and product selectivity among different copper supported silica appears to be a complex function of acidity and the nature of copper species in the Cu–SiO2catalysts. No direct correlation was observed between a specific catalyst property such as acidity and pore size, and the performance of the Cu–SiO2catalysts. From the characterization, it appears that the species responsible for higher activity and selectivity to GVL are monomeric partially oxidized copper species in a strong interaction with the support in combination with a higher number of acid sites, both of which are present in Cu–SiO2-Q6. Cu–SiO2-Q6 showed the highest conversion and selectivity of 66 and 81%, respectively, under optimized conditions.