Dual‐Electrode Catalytic Engineering for Sustainable C─C Bond Construction via Paired Electrochemical α‐Alkylation of Nitriles

Efficient paired electrochemical synthesis requires precise synchronization between anodic intermediate generation and cathodic consumption. However, uncontrolled adsorption and mismatched reaction kinetics often result in intermediate accumulation and competing side reactions. Here, we address this challenge through interfacial regulation of both anodic and cathodic catalysts, enabling a synchronized electrocatalytic platform for α‐alkylation of nitriles using alcohols as sustainable alkyl sources. An Fe‐doped NiO anode and Pb/C cathode are rationally integrated to regulate alcohol oxidation, carbon–carbon coupling, and selective C═C hydrogenation. Fe incorporation tailors the electronic structure and adsorption behavior of Ni sites, accelerating alcohol activation while mitigating nitrile‐induced inhibition, whereas Pb/C selectively promotes alkene hydrogenation without affecting nitrile functionalities. The optimized paired system achieves 91.68% yield and >99% conversion for 2,3‐diphenylpropionitrile at 20 mA cm −2 , enabling continuous and efficient synthesis across a broad range of aromatic and aliphatic alcohols with excellent functional‐group tolerance and robust operational stability. This work provides a general catalyst design principle for paired electrochemical synthesis by coordinating interfacial reaction kinetics and intermediate flux between two electrodes.