Infrared (IR) light photo-thermocatalysis has been motivated by the realization of prospects that sunlight is an inexhaustible energy source where infrared photons most strongly emitted in the solar spectrum are converted into thermal energy, which thus can drive different redox catalysis applications, e.g., oxidative degradation of volatile organic compounds (VOCs). Herein, we report that the hybrid nanomaterial Pt-rGO-TiO2, featuring the broad light wavelength absorption (800–2500 nm), can be used as a highly active photo-thermal responsive catalyst for efficient VOCs decomposition under IR irradiation. The maximum photo-thermal conversion efficiency is able to reach 14.1% with a significant toluene conversion of 95% and CO2 yield of 72% under infrared irradiation intensity of 116 mW/cm2, along with retaining its stability for nearly 50 h. The comparison characterizations evidence that such excellent performance is predominantly attributed to the synergistic effects of efficient light-to-heat conversion, increased adsorption capacity and well dispersed supported Pt-TiO2 catalyst on the 2D rGO sheet. This work highlights that graphene-based composites as IR light photon absorber show great promise for redox reactions through photo-thermal effect, which provides an alternative and feasible strategy for solar energy conversion.