Fe acts as the active site and Cu acts as the activity promoter to improve Fe activity in Cu/Fe–NC for higher CO2 reduction reaction performance to multi-electron C1 products. Display omitted •Dual-atom center enhances the multi-electron pathways for CO2 RR.•Cu/Fe‒NC exhibits low limiting potentials for multi-electron C1 products.•The synergistic effect of Cu/Fe can improve Fe atom catalytic activity.•Dual-atom regulation is conducive to design high atomically dispersed electrocatalysts. Single-atom catalysts (SACs) are promising electrocatalysts for CO2 reduction reaction (CO2RR) due to the maximal atomic utilization and high catalytic activity. However, most reported SACs tend to convert CO2 to CO or HCOOH rather than other multi-electron C1 products. Here, Taking the regular Fe single-atom catalyst (Fe-NC) as a probe, our study revealed that the construction of dual-atom center through additional Cu (Cu/Fe-NC) allowed for CO2RR proceeding via multi-electron pathways to generate CH3OH and CH4 by means of density functional theory. Cu/Fe-NC exhibited low limiting potentials of −0.42, −0.51, and −0.51 V for HCOOH, CH3OH, and CH4, respectively, while a high limiting potential of −1.18 V for CO. In CO2RR process, using the synergistic effect, Fe acts as the active site and Cu acts as the activity promoter to improve Fe activity for stronger adsorption ability, which promotes the generation of multi-electron products. Hence, the Cu, Fe dual-atom center might provide better catalytic site than regular Fe single-atom center in CO2RR. This work demonstrated Cu/Fe-NC as a high performance CO2RR catalyst to multi-electron products, which will guide more experimental research in high atomically dispersed electrocatalysts to promote CO2RR to high economic value products.