This study uses a facile aerosol-assisted method to synthesize mesoporous Cu/ZnO-ZrO2 catalysts, with superior thermal and photothermal performance for CO2 reduction to methanol. The process is based on forming an aerosol from Zn and Zr precursors and a surfactant solution. Then, fast drying of the droplets was used to obtain the ZnO-ZrO2 support with uniform nanoparticles and 6 nm calibrated mesopores. After impregnation with Cu species, the Cu/ZnO-ZrO2 catalyst exhibited high activity for the targeted reaction, as shown by the high TOFCu values and superior methanol yields and selectivity. Extensive characterization, such as BET, TEM, and photocurrents, confirms the abundant mesopores and relatively high surface area of the ZnO-ZrO2 support synthesized by the aerosol-assisted surfactant method, thus promoting Cu dispersion as well as enhancing the localized surface plasmon resonance (LPSR) effect to generate efficient currents and change the chemical state of Cu by in situ oxidation and reduction to promote a hydrogen overflow effect under visible light irradiation. Therefore, the simple and scalable aerosol-assisted process presented in this study provides new insight into the fabrication of composite mesoporous oxide as a promising photothermal catalyst.