Oxophilicity‐Driven Potential Window Engineering Enables Scalable and Low‐Emission Paired Electrosynthesis on Asymmetric CuO x @Ag Platform

Paired electrochemical valorization reactions (EVRs) offer a sustainable route for co‐producing value‐added chemicals, yet their efficiency is hindered by overlapping potential windows with water electrolysis reactions (WER). Here, an asymmetric CuOx@Ag electrocatalyst platform is proposed that decouples both anodic and cathodic EVRs from WER via Ag‐mediated oxophilicity modulation. Atomic‐level Ag incorporation suppresses *OH/H 2 O adsorption and widens the potential windows to 422 mV (anode) and 502 mV (cathode) in a glycerol oxidation | 4‐nitrophenol reduction pair. The system achieves > 90% Faradaic efficiency and > 70 mmol h −1 cm −2 productivity. In situ and DFT analyses reveal that Ag‐induced weakening of Cu–O interactions underlies the WER suppression mechanism. Techno‐economic and life‐cycle evaluations indicate 31.6% cost reduction and 57.4% lower CO 2 emissions versus thermochemical routes. The CuO x @Ag platform thus provides a scalable and general strategy for low‐carbon electrosynthesis across diverse redox systems.