The advent of atomically precise metal nanoclusters (NCs) has effectively bridged the gap between single-atom and conventional nanoparticle catalysts. Metal NCs have been widely used as highly efficient electrocatalysts, offering an ideal platform for probing catalytic mechanisms at the atomic level, as all atoms, from the metal core to surface ligands, are clearly resolved. Bimetallic NCs usually exhibit better catalytic performance than their monometallic counterparts because of the synergistic catalytic effect. Among them, AgCu NCs stand out as promising model catalysts owing to their relatively low cost compared with Au, Pt, and Pd, rich structural diversity, and broad spectrum of catalytic applications. These attributes render them not only exemplary model catalysts for fundamental research but also highly promising electrocatalysts for complex reactions that can generate highly valuable chemicals. This review provides a comprehensive overview of recent advances in the structure and electrocatalytic applications of atomically precise AgCu NCs. First, structurally defined archetypes are summarized, and then their exemplary performance in key electrocatalytic processes, including carbon dioxide reduction, nitrate reduction, and C–N bond formation, is discussed, with a focus on the unique synergistic role of the bimetallic structure in enhancing activity, selectivity, and stability. Finally, pathways for the rational design of electrocatalysts based on next-generation AgCu NCs for sustainable energy development and the synthesis of valuable chemicals are outlined.