Beyond C ₁ Products: How Single‐Atom Catalysts Contribute to Solar‐Driven CO ₂ Reduction into C ₂₊ Hydrocarbons

Abstract Single‐atom catalysts (SACs) have demonstrated their potential in photocatalytic CO ₂ reduction due to their fascinating properties and well‐defined structure for forecasting the mechanism. Although remarkable progress has been achieved in enhancing SAC activity, the selective formation of C ₂₊ hydrocarbons with higher energy densities remains a significant challenge, primarily due to the inherent limitations of isolated single‐active sites in simultaneously enabling CO ₂ adsorption, activation, and C─C coupling. Therefore, in this review, recent advances in SAC‐based strategies for promoting C ₂₊ hydrocarbons production are summarized, with a particular focus on dual single‐atom catalysts and hybrid SAC systems. The introduction of dual metal sites with tunable electronic structures and charge distributions is discussed can stabilize key intermediates ( ^* CO, ^* CHO), mitigate electrostatic repulsion, enhance intermediate collision probability, influence intermediate adsorption configurations, and ultimately facilitate C─C coupling. By offering insights into the design principles, mechanistic pathways, and characterization techniques, this review aims to motivate future efforts toward the rational design of highly selective and efficient systems for solar‐driven CO ₂ reduction into C ₂₊ hydrocarbons.