Abstract Developing efficient and durable Pt‐based catalysts via interface engineering remains a critical yet challenging task for water electrolysis under high‐pH conditions. Herein, we design a unique asymmetric Pt─O─Cu ligand at the PtCu 2 (111)/CuO(002) heterojunction interface to promote alkaline HER kinetics. This ligand balances the adsorption and desorption of H* on the Pt site by accelerating electron transfer at the interface while enhancing the adsorption of H 2 O on the Cu site. Moreover, the strong d‐d/sp hybridization and more delocalized d‐DOS located at the Pt─O─Cu ligand enhance the interatomic interactions, which helps alleviate the dissolution and agglomeration of Pt and Cu atoms. As anticipated, the PtCu 2 /CuO requires ultra‐low overpotentials of 10, 14 and 47 mV in, respectively, alkaline, acidic and neutral electrolytes to achieve a current density of 10 mA cm −2 . Even more surprising is that the PtCu 2 /CuO||RuO 2 dual‐electrode hydrolysis cell can stably operate at a high current density of 1 A cm −2 for more than 500 h in a simulated industrial environment, demonstrating significant potential for industrial applications. This work provides a new paradigm for the design of industrially relevant high‐performance Pt‐based alkaline hydrogen evolution catalytic materials.