Indoor toxic volatile organic compounds (VOCs) pollution is a serious threat to people’s health and toluene is a typical representative. In this study, we developed a composite photocatalyst of carbon nitride quantum dots (CNQDs) in situ-doped TiO2 inverse opal TiO2 IO for efficient degradation of toluene. The catalyst was fabricated using a sol-gel method with colloidal photonic crystals as the template. The as-prepared catalyst exhibited excellent photocatalytic performance for degradation of toluene. After 6 h of simulated sunlight irradiation, 93% of toluene can be converted into non-toxic products CO2 and H2O, while only 37% of toluene is degraded over commercial P25 in the same condition. This greatly enhanced photocatalytic activity results from two aspects: (i) the inverse opal structure enhances the light harvesting while providing adequate surface area for effective oxidation reactions; (ii) the incorporation of CNQDs in the framework of TiO2 increases visible light absorption and promotes the separation of photo-generated charges. Collectively, highly efficient photocatalytic degradation of toluene has been achieved. In addition, it can be expanded to efficient degradation of organic pollutants in liquid phase such as phenol and Rhodamine B. This study provides a green, energy saving solution for indoor toxic VOCs removal as well as for the treatment of organic wastewater