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With the development of the world economy and the rapid advancement of global industrialization, the demand for energy continues to grow. The significant consumption of fossil fuels, such as oil, coal, and natural gas, has led to excessive carbon dioxide emissions, causing global ecological problems. CO₂ hydrogenation technology can convert CO₂ into high-value chemicals and is considered one of the potential ways to solve the problem of CO₂ emissions. Metal/semiconductor catalysts have shown good activity in carbon dioxide hydrogenation reactions and have attracted widespread attention. Therefore, we summarize the recent research on metal/semiconductor catalysts for photocatalytic CO₂ hydrogenation from the design of catalysts to the structure of active sites and mechanistic investigations, and the internal mechanism of the enhanced activity is elaborated to give guidance for the design of highly active catalysts. Finally, based on a good understanding of the above issues, this review looks forward to the development of future CO₂ hydrogenation catalysts.