Abstract: The environmental crisis triggered by the dramatic surge in anthropogenic CO₂ emissions has accelerated the development of carbon neutrality technologies. Among these, CO₂ hydrogenation to methanol has garnered significant attention due to its triple potential for carbon emission reduction, green hydrogen energy storage, and high-value-added chemical conversion. However, its industrial application remains constrained by the development of efficient catalysts and comprehensive understanding of reaction mechanisms. This review systematically focuses on non-noble metal catalytic systems with promising industrial prospects, summarizing the latest advances in their thermodynamic pathways, catalyst material design, and reaction mechanisms. Key findings reveal that Cu-based catalysts demonstrate enhanced active site density and oxygen vacancy regeneration through optimized active site configuration and interface engineering. In₂O₃-based catalysts exhibit superior performance owing to their exceptional oxygen vacancy stability and anti-sintering characteristics. Zr-based solid solution catalysts, meanwhile, optimize electronic structures via the synergistic effect of lattice stress and oxygen vacancies, overcoming the performance limitations of single-component catalysts. Moreover, key optimization directions have been identified: specific surface area and Lewis acid-base sites of supports, selection of promoters and their electron transfer functions, and preparation strategies for precise regulation of metallic active sites. Mechanistic studies combining experimental and theoretical approaches unveil a competitive relationship between the formate pathway （dominated by *HCOO intermediates） and the reverse water-gas shift-carbonylation pathway （governed by *COOH dissociation）, with pathway dominance strongly correlated to catalyst structural characteristics. By integrating multiscale catalyst design with interfacial properties and kinetic behavior analysis, this review provides theoretical guidance for constructing efficient CO₂-to-methanol conversion systems. It advances the integration of carbon cycling technologies with green hydrogen economy, offering valuable insights for developing energy-environment synergistic technologies under carbon neutrality objectives.