<p>Overcoming the limitations of restricted solar-spectrum harvesting and rapid recombination of photogenerated charge carriers is critical for advancing the efficiency of artificial photosynthetic CO₂ reduction. Herein, we report a solvothermally synthesized ZnO/CeZrO₂ heterojunction photothermal catalyst designed to address these bottlenecks. Comprehensive structural analyses confirm the formation of an intimate heterointerface, which optimizes band alignment and markedly enhances charge-carrier separation and transport. Under concentrated solar irradiation—where strong photothermal coupling occurs—the optimized 8 wt% ZnO/CeZrO₂ catalyst achieves exceptional activity, yielding CO and CH₄ production rates of 305.2 and 220.7&#xa0;μmol·g⁻¹·h⁻¹, respectively. These values represent 51-fold and 72-fold enhancements relative to performance under unconcentrated irradiation. Mechanistic investigation reveals that photothermal synergy substantially lowers the reaction barrier, reducing the apparent activation energy (<i>E</i>ₐ) from 17.36 to 12.98&#xa0;kJ·mol⁻¹. Electrochemical analyses further confirm the superior charge-transport properties of the heterojunction. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) identifies key intermediates (^*COOH, ^*CO, ^*CHO, ^*CH₂, and ^*CH₃), elucidating the stepwise hydrogenation pathway for the conversion of CO₂ to CH₄. These results demonstrate that integrating heterojunction band engineering with photothermal coupling significantly enhances CO₂ reduction performance and offers a promising route toward efficient solar-to-fuel conversion.</p>