The integration of organometallic compounds with metal nanoparticles can, in principle, generate hybrid nanocatalysts endowed with augmented functionality, presenting substantial promise for catalytic applications. Herein, we synthesize an atomically precise metal cluster (Ag9Cu6) catalyst integrated with alkynylferrocene molecules (Ag9Cu6‐Fc). This hybrid catalyst design facilitates a continuous electron transfer channel via an ethynyl bridge and establishes a distinctive local chemical environment, resulting in remarkably enhanced catalytic activity in CO2 electroreduction. The Ag9Cu6‐Fc catalyst achieves a record‐high product selectivity of CO Faradaic efficiency of 100% and an industrial‐level CO partial current density of –680 mA/cm2, surpassing the performance of the Ag9Cu6 cluster (62% and –230 mA/cm2, respectively) without ferrocene functionalization in a membrane electrode assembly cell. Operando experimental and computational findings offer valuable insights into the role of ferrocene functionalization in synergistically improving the catalytic performance of metal clusters, propelling the advancement of metallic‐organometallic hybrid nanoparticles for energy conversion technologies.