LAUSR

Dual‐atom catalysts (DACs) with two adjacent atomic centers can operate together, offering complementary or synergistic effects or both, outperforming single‐atom catalysts (SACs). However, their rational design and precise synthesis remain significant challenges. Herein, atomically dispersed Fe and Se dual atomic sites are reported with asymmetric coordination supported on porous nitrogen‐doped carbon nanofibers (Fe/Se─N─C), engineered for highly efficient CO2 electroreduction. The asymmetrically coordinated catalyst achieves an impressive CO Faradaic efficiency of 95.6% at −0.45 V versus reversible hydrogen electrode. When assembled in a gas diffusion electrode, Fe/Se─N─C exhibits an exceptionally high CO partial current density of 272 mA cm‒2 in flow‐cell. Furthermore, Fe/Se─N─C‐based membrane electrode assembly (MEA) presents a remarkable 99% faradaic efficiency for CO2‐to‐CO conversion at an industrial‐level current density of 250 mA cm−2. Both in situ characterizations and theoretical calculations prove that the electronic hybridization effect induced by asymmetrically coordinated Fe‐Se dual sites effectively regulates the adsorption/desorption kinetic process of key intermediates on the active centers, breaks the linear scaling relationship between COOH* and CO* intermediates, and enhances the activation of CO2 and the desorption of CO.