Solar-driven catalytic conversion of carbon dioxide (CO) into value-added C chemicals and fuels has attracted significant attention over the past decades, propelled by urgent environmental and energy demands. However, the catalytic reduction of CO continues to face significant challenges due to inherently slow reduction kinetics. This review traces the historical development and current state of photothermal CO reduction, detailing the mechanisms by which CO is transformed into C products. A key focus is on catalyst design, emphasizing surface defect engineering, bifunctional active site and co-catalyst coupling to enhance the efficiency and selectivity of solar-driven C synthesis. Key reaction pathways to both C and C products are discussed, ranging from CO, CH and methanol (CHOH) synthesis to the production of C products such as C hydrocarbons, ethanol, acetic acid, and various carbonates. Notably, the advanced synthesis of C hydrocarbons exemplifies the remarkable potential of photothermal technologies to effectively upgrade CO-derived products, thereby delivering sustainable liquid fuels. This review provides a comprehensive overview of fundamental mechanisms, recent breakthroughs, and pathway optimizations, culminating in valuable insights for future research and industrial-scale prospect of photothermal CO reduction.