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The direct hydrogenation of greenhouse gas CO₂ to higher alcohols (C₂₊OH) provides a new route for the production of high-value chemicals. Due to the difficulty of C-C coupling, the formation of higher alcohols is more difficult compared to that of other compounds. In this review, we summarize recent advances in the development of multifunctional catalysts, including noble metal catalysts, Co-based catalysts, Cu-based catalysts, Fe-based catalysts, and tandem catalysts for the direct hydrogenation of CO₂ to higher alcohols. Possible reaction mechanisms are discussed based on the structure–activity relationship of the catalysts. The reaction-coupling strategy holds great potential to regulate the reaction network. The effects of the reaction conditions on CO₂ hydrogenation are also analyzed. Finally, we discuss the challenges and potential opportunities for the further development of direct CO₂ hydrogenation to higher alcohols.