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Among the possible products, multi\u2010carbon (C<jats:sub>2+<\/jats:sub>) compounds such as ethylene and ethanol are highly desirable due to their higher energy density and industrial relevance. Recently, single\u2010atom catalysts (SACs) have emerged as a powerful class of electrocatalysts in CO<jats:sub>2<\/jats:sub>RR, offering high atomic efficiency and tunable active sites. However, challenges such as sluggish C\u2500C coupling kinetics, dynamic evolution of the catalytic sites, limited understanding of reaction mechanism, and difficulties at controlling product selectivity hinder their further development for large\u2010scale application. Hence, this review explores the underlying mechanisms for CO<jats:sub>2<\/jats:sub> to C<jats:sub>2+<\/jats:sub> product conversion, emphasizing catalyst design strategies to enhance C\u2500C coupling efficiency and selectivity. Furthermore, recent advances in in situ characterization techniques that provide atomic\u2010level insights into reaction intermediates and active site evolution are discussed. Finally, the potential of machine learning approaches in accelerating catalysts discovery by optimizing SACs structures, identifying key design parameters, and predicting catalytic performance is highlighted. 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