Recent Advances in Atomically Precise Silver Clusters Applied for Electrocatalysis: From Synthesis and Structure to Catalysis

Atomically precise silver nanoclusters with discrete and crystallographically resolved structures are emerging as a versatile platform to bridge nanoscience and electrocatalysis. Their designable metal cluster cores, ligand shells, and higher order assemblies enable systematic regulation of electronic structure, active‐site accessibility, and interfacial microenvironments, offering opportunities to mitigate intrinsic limitations of bulk Ag (e.g., weak intermediate adsorption and competition of side reactions). Yet, the controllable synthesis of well‐defined Ag clusters remains challenging, and potential‐driven operando evolution also complicates the identification of true working active motifs. In this review, we summarize recent advances in the synthesis and structural modulation of atomically precise Ag clusters, and highlight representative electrocatalytic applications in oxygen reduction reaction, CO 2 RR, hydrogen evolution reaction, and electrocatalytic hydrogenation. Particular emphasis is placed on ligand‐shell engineering (lability, steric effect, and surface coverage), support coupling/defect effects, and operando activation or reconstruction that collectively govern the activity, selectivity, and durability of catalysts. We hope this overview provides practical guidance and design inspiration to develop silver cluster‐based electrocatalysts and to establish clear relationships between structure/interface and performance in this rapidly developing field.