Structural Asymmetric Regulation in Metal‐Organic Frameworks for Efficient Electrocatalytic CO ₂ to C ₂ Products

Electrocatalytic CO 2 reduction reaction (CO 2 RR) to value‐added C 2 products is a promising pathway for sustainable chemical manufacturing and carbon resource valorization, yet its efficiency remains limited by the intrinsically sluggish C─C coupling step. Herein, we report a structural asymmetric regulation strategy to precisely manipulate the local coordination environment of Cu sites in metal–organic frameworks (MOFs). Remarkably, the as‐prepared monomethyl‐mediated Cu‐MOF catalyst (Cu‐Me‐tp) achieves a high Faradaic efficiency of 93.1% for C 2 products at a current density of 540 mA cm −2 and maintains excellent stability over 100 h of continuous operation. In situ spectroscopic analyses combined with computational calculations reveal that the structural asymmetry induces local electronic anisotropy at Cu sites, resulting in a shift of * CO adsorption from atop to bridge configuration. This adsorption transformation significantly reduces the C─C coupling barrier by 0.74 eV and lowers the desorption energies of C 2 products to below 0.20 eV, which thereby promotes an efficient C 2 ‐selective CO 2 RR process.