In summary, this work pioneers the design of NHC-capped bimetallic nanoclusters through a kinetically controlled synthesis strategy, overcoming traditional limitations in ligand sensitivity and expanding the frontier of alloy cluster chemistry. By integrating atomic-level structural analysis with DFT-guided electronic insights, it establishes a direct link between NHC-induced electron delocalization and enhanced thermal/optical stability, while demonstrating unprecedented catalytic efficiency in sustainable urea electrosynthesis. This breakthrough not only enriches the NHC-protected nanocluster database but also opens avenues for rational engineering of multifunctional nanomaterials in energy conversion and environmental remediation.