The electronic interaction between metal and support plays a significant role in varying catalytic activity of oxide-supported metal catalysts for the aerobic oxidation of biomass-based alcohols and aldehydes. Employing Y3+-doped ceria supported Pt catalysts, Pt/Ce1-xYxO2-δ, different interfacial atomic structures, including Pt/Ce-Vo(-Ce)2, Pt/Y-Vo(-Ce)2, Pt/Ce-Vo(-Y)2, and Pt/Y-Vo(-Y)2 (Vo represents an oxygen vacancy), were created in this work to modulate the interfacial electron transfer capacity. The results of experimental and theoretical investigations showed that the Pt/Y-Vo(-Ce)2 interfacial structure owned the highest electron transfer capacity from Pt to the support, resulting in more Ptδ+/Y-Vo(-Ce)2 sites. Accordingly, the catalyst Pt/Ce0.75Y0.25O2-δ owning the largest amount of Ptδ+/Y-Vo(-Ce)2 sites exhibited notably promoted catalytic activity for the oxidation of 5-hydroxymethylfurfural (HMF) toward 2,5-furandicarboxylic acid (FDCA), affording a complete conversion of HMF and 96.6% yield of FDCA in 6 h. This work provided a facile and versatile strategy to modulate the electron transfer capacity of oxide supported metal catalysts by manipulating the interfacial atomic structure for promoting their activities in various catalytic oxidation reactions.