The escalating demand for sustainable nitrogen-containing chemicals calls for transformative electrocatalytic strategies that can precisely orchestrate C-N bond formation. Atomically defined metal nanoclusters have emerged as a frontier in electrocatalysis, enabling the direct synthesis of chemicals via C-N coupling. Their discrete electronic structures and tunable ligand environments permit atomic-level control over adsorption, activation, and proton-electron transfer dynamics, overcoming the intrinsic kinetic and thermodynamic challenges of multi-electron C-N coupling reactions. Here, we present a comprehensive overview of cluster-based electrocatalysts, encompassing cluster properties, synthetic routes, mechanistic insights, performance descriptors critical for evaluating catalytic efficiency, and their applications in the synthesis of urea, ammonia, amines, amides, oximes, and amino acids. We focus on the correlations between cluster composition, size, and local coordination in dictating product distribution and catalytic durability. Finally, we identify current bottlenecks in stability, scalability, and industrial integration, and propose rational design principles for engineering next-generation clusters to achieve sustainable, high-value nitrogen chemical production. This review frames a roadmap for exploiting atomic precision in electrocatalysis, charting a path toward transformative C-N bond-forming technologies.
