Simultaneous High Current Density and Selective Electrocatalytic CO₂‐to‐CH₄ through Intermediate Balancing

Abstract The electrochemical reduction of CO 2 to CH 4 is promising for carbon neutrality and renewable energy storage but confronts low CH 4 selectivity, especially at high current densities. The key challenge lies in promoting *CO intermediate and *H coupling while minimizing side reactions including C−C coupling and H−H coupling, which is particularly difficult at high current density due to abundant intermediates. Here we report a cooperative strategy to address this challenge using Cu‐based catalysts comprising Cu−N coordination polymer and CuO component that can simultaneously manage the key intermediates *CO and *H. A fast CO 2 ‐to‐CH 4 conversion rate of 3.14 mmol cm −2 h −1 is achieved at 1,300 mA cm −2 with a Faradaic efficiency of 51.7 %. In situ spectroscopy and theoretical calculations show that the increased Cu−Cu distance in the Cu−N coordination polymer component favors multistep *CO hydrogenation over the dimerization, and the CuO component ensures an adequate supply of *H, together contributing to the selective CO 2 ‐to‐CH 4 conversion at high current densities. This work develops a cooperative strategy for the electrosynthesis of CH 4 with simultaneous high current density and high selectivity by rational catalyst design, paving the way for its applications.