Metal‐π Sites Localized Hydrogen‐*CO Coupling for Enhanced CO ₂ Electromethanation

Electrochemical CO 2 ‐to‐CH 4 conversion on Cu–N–C single‐atom catalysts is fundamentally limited by *H/*CO spatial mismatch from numerous metal‐free CN matrix, where the long‐range hydrogen transfer easily causes *H coupling or *CO dimerization, ultimately impeding *CHO formation. Herein, we design a two‐dimensional metal–organic polymer catalyst featuring spatially adjacent Cu and 1H‐benzotriazole to form Cu‐π units, which achieves a Faradaic efficiency of 61% for CH 4 at 800 mA·cm −2 . Using Infrared free‐electron laser (IRFEL) nanospectroscopy, we identify the key Cu‐π coordination environment and low‐frequency bonding modes, unavailable by conventional IR techniques. Complementary in‐situ synchrotron radiation IR, electrochemical experiments and theoretical calculations reveal that π sites adsorb hydrated cations, enabling localized hydrogen supply to adjacent *CO on Cu sites and suppressing long‐range hydrogen transfer‐induced side reactions. This inorganic–organic synergy paves a new pathway to spatially match *H and *CO, advancing efficient CO 2 ‐to‐hydrocarbons conversion.