Single-atom catalysts characterized by their novel electronic configurations and exceptional atomic utilization efficiency have emerged as potential alternatives to costly noble metal catalysts, garnering extensive research attention in various electrocatalytic fields. However, the inherent characteristics of single metal centers constrain their further application in catalyzing multi-electron reactions. In contrast, multi-atom catalysts (MACs), particularly dual-atom catalysts (DACs), possess multiple active metal sites that can significantly enhance catalytic performance through synergistic effects. This review summarizes recent developments in multi-atom catalysts, focusing on synthesis methods, design strategies, and the correlation between interatomic synergy and catalytic efficiency. Furthermore, we discuss their applications in key electrochemical reactions, including the hydrogen evolution reaction, oxygen reduction reaction, and oxygen evolution reaction. Finally, we outline the opportunities and challenges in this field to guide the development of high-efficiency catalysts for sustainable energy conversion applications.