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Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO 2 RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe-S 1 N 3 ), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34 h -1 ), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self-relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO 2 RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships., (© 2023 Wiley-VCH GmbH.)