The prerequisite for electrocatalytic hydrogenation reactions (EHRs) is H2O splitting to form surface hydrogen species (*H), which occupy catalytic sites and lead to mismatched coverage of *H and reactants, resulting in unsatisfactory activity and selectivity. Thus, modulating the splitting pathway of H2O is significant for optimizing the EHR process. Herein, a Cu−Ag alloy with a superlattice structure of staggered‐ordered Cu and Ag is theoretically predicted and experimentally proven to undergo a pathway for H2O splitting called the hydrogen transfer reaction (HTR) in the water layer, which involves the formation of *H, the capture of *H by a water cluster to form H*(H2O)x and subsequent hydrogenation reactions by H*(H2O)x. Taking acetylene hydrogenation as a model case, the as‐proposed HTR pathway could lead to a relaxation hydrogenation process to modulate the matching degree of C2H2 and *H, thus enabling a 91.2 % C2H4 Faradaic efficiency at a partial current density of 0.38 A cm−2, greatly outperforming its counterpart without a superlattice structure. [ABSTRACT FROM AUTHOR]

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