Volatile organic compounds (VOCs) are ubiquitous organic pollutants affecting atmospheric environment and human health. The development of new efficient and environmentally friendly materials utilizing photothermal synergistic catalysis for purification of VOCs is still challenging. Herein, we design and prepare a core–shell TiN@TiO₂ nanostructure integrating with nanoscaled Pt (Pt/[TiN@TiO₂]) by an attractive quenching method. The strong light-harvesting capability of Pt and TiN components improve light-to-heat utilization efficiency by their intrinsic surface plasmon resonance effect. The TiO₂ component upon the surface and the coexisting coupling effect of Pt⁰ and Pt²⁺ enhance the photocatalytic effect of the system. As a result, the catalytic performance is significantly improved with toluene (120 ppm) conversion of 100% under the gas hourly space velocity of 72,000 mL·g⁻¹·h⁻¹ and light illumination of 500 mW·cm⁻². The desired catalyst thus achieves highly efficient coupling effect of photocatalysis and light-to-heat conversion for promoting VOCs abatement.