High-efficiency, low-temperature, durable catalysts are regarded as promising tools for oxidizing volatile organic compounds (VOCs). In this study, we design an alternative core/shell structure with inert porous SiO2 nanoparticles decorated with Pt nanoparticles as the core and an ultrathin ZrO2 layer as the shell (SiO(2)pPt@ZrO2), where the average thickness of the ZrO2 shell is 6 nm. The close three-dimensional contact between the Pt nanoparticles and the ZrO2 shell maximizes the metal-support interaction and enables strong electronic interactions. Consequently, the as-prepared samples show superior charge separation, thermal stability, and reactive oxygen generation capacity. Photothermal synergetic catalytic activity is demonstrated via the toluene oxidation reaction, and it is found that toluene can be completely oxidized within 1 h of light illumination at 150 degrees C, compared to 80% oxidation under the same conditions without light illumination. The results provide insight into the design of high-performance catalysts of refractory VOCs.