This study investigates the site-distance effect of Fe–Rh atoms in oxygen reduction reaction (ORR) catalysts. The research demonstrates that the distance between Fe and Rh atoms significantly influences the catalytic performance of Fe–Rh x @NC catalysts. Theoretical calculations and experimental results show that an optimal Fe–Rh distance (dFe-Rh) enhances the catalyst's ORR activity. Bader charge analysis reveals that the interaction between Fe and Rh atoms at a certain distance alters the catalytic electronic structure, optimizing the catalyst's adsorption strength. The Fe–Rh2@NC catalyst, with the optimal dFe-Rh, exhibits a half-wave potential of 0.91 V, higher than that of commercial Pt/C (0.86 V). This study emphasizes the importance of understanding the site-distance effect in dissimilar metal atoms catalysts for designing efficient catalyst systems. The research highlights the role of atomic distance regulation in catalysis, particularly in enhancing ORR performance. The study combines theoretical calculations with experimental synthesis to systematically investigate the site-distance effect of Fe–Rh atom catalysts supported by N-doped graphene. DFT calculations predict that the site-distance effect changes the catalytic electronic structure of different Fe–Rh atomic site distances, optimizing the catalyst's adsorption strength. The Fe–Rh2@NC catalyst, with the optimal atomic distance, provides a half-wave potential of 0.91 V, demonstrating its superior ORR activity. XPS and XAS confirm the effect of site-distance on the interaction strength between Fe and Rh. DFT calculations show that Fe–Rh2@NC can interact with O2 moderately, with suitable adsorption energy, promoting the kinetic process of ORR. This study provides insights into the design of high-performance atomic catalysts for practical applications.This study investigates the site-distance effect of Fe–Rh atoms in oxygen reduction reaction (ORR) catalysts. The research demonstrates that the distance between Fe and Rh atoms significantly influences the catalytic performance of Fe–Rh x @NC catalysts. Theoretical calculations and experimental results show that an optimal Fe–Rh distance (dFe-Rh) enhances the catalyst's ORR activity. Bader charge analysis reveals that the interaction between Fe and Rh atoms at a certain distance alters the catalytic electronic structure, optimizing the catalyst's adsorption strength. The Fe–Rh2@NC catalyst, with the optimal dFe-Rh, exhibits a half-wave potential of 0.91 V, higher than that of commercial Pt/C (0.86 V). This study emphasizes the importance of understanding the site-distance effect in dissimilar metal atoms catalysts for designing efficient catalyst systems. The research highlights the role of atomic distance regulation in catalysis, particularly in enhancing ORR performance. The study combines theoretical calculations with experimental synthesis to systematically investigate the site-distance effect of Fe–Rh atom catalysts supported by N-doped graphene. DFT calculations predict that the site-distance effect changes the catalytic electronic structure of different Fe–Rh atomic site distances, optimizing the catalyst's adsorption strength. The Fe–Rh2@NC catalyst, with the optimal atomic distance, provides a half-wave potential of 0.91 V, demonstrating its superior ORR activity. XPS and XAS confirm the effect of site-distance on the interaction strength between Fe and Rh. DFT calculations show that Fe–Rh2@NC can interact with O2 moderately, with suitable adsorption energy, promoting the kinetic process of ORR. This study provides insights into the design of high-performance atomic catalysts for practical applications.