Abstract
This article presents a systematic review and establishes a fundamental distinction between two primary technological pathways for catalytic carbon dioxide (CO 2 ) conversion: thermocatalytic conversion and electrocatalytic reduction. Within thermocatalytic pathway, the application of heterogeneous catalysts and homogeneous molecular catalysts in reactions such as CO 2 hydrogenation and dry reforming has been discussed. It details strategies for optimizing CO 2 activation and selective hydrogenation through the design of active sites (e.g., metal–support interfaces, oxygen vacancies) and ligand environments, while examining prevalent catalyst deactivation mechanisms. For the electrocatalytic pathway, the focus is on renewable energy‐driven electrochemical CO 2 reduction. The article summarizes the design of key electrode materials, highlighting how nanostructuring, alloying, and management of the local reaction microenvironment can achieve high selectivity toward either C1 or C2+ products. Advances in device engineering, such as membrane electrode assemblies, are also discussed. Furthermore, the unique role of single‐atom catalysts as a bridge between homogeneous and heterogeneous systems, demonstrating advantages across both pathways, has been elucidated. Finally, the article contrasts the common and distinct challenges facing the industrialization of these two routes and concludes by underscoring the importance of multidisciplinary integration in designing next‐generation high‐performance catalysts to accelerate the commercialization of CO 2 conversion technologies.