This article presents a study on the regulation of atomic Fe–Rh site distance for enhancing the efficiency of the oxygen reduction reaction (ORR). The research highlights the importance of the site-distance effect in single-atom catalysts (SACs), particularly for Fe–Rh@NC catalysts. Through theoretical and experimental approaches, the study demonstrates that the distance between Fe and Rh atoms significantly influences the catalytic performance of the catalyst. Bader charge analysis reveals that the interaction between Fe and Rh atoms at an optimal atomic distance (dFe–Rh) alters the electronic structure of the catalyst, optimizing the adsorption strength for ORR. The researchers designed and synthesized Fe–Rh@NC catalysts using a spatial confinement strategy, achieving an optimal dFe–Rh that enhances the catalyst's intrinsic ORR activity. The catalyst exhibits a half-wave potential of 0.91 V, surpassing that of commercial Pt/C (0.86 V). The study emphasizes the critical role of determining the site-distance effect in dissimilar metal atoms catalysts for the design of efficient catalyst systems. Density functional theory (DFT) calculations and experimental characterizations, including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), support the findings. The results show that the site-distance effect influences the interaction strength between Fe and Rh atoms, which is crucial for the ORR process. The study underscores the importance of precise control over atomic distances in SACs to achieve high-performance electrocatalysts for practical applications. The findings contribute to the understanding of how atomic distance regulation can enhance the catalytic activity of SACs, offering a promising strategy for the development of efficient and cost-effective catalysts for ORR.This article presents a study on the regulation of atomic Fe–Rh site distance for enhancing the efficiency of the oxygen reduction reaction (ORR). The research highlights the importance of the site-distance effect in single-atom catalysts (SACs), particularly for Fe–Rh@NC catalysts. Through theoretical and experimental approaches, the study demonstrates that the distance between Fe and Rh atoms significantly influences the catalytic performance of the catalyst. Bader charge analysis reveals that the interaction between Fe and Rh atoms at an optimal atomic distance (dFe–Rh) alters the electronic structure of the catalyst, optimizing the adsorption strength for ORR. The researchers designed and synthesized Fe–Rh@NC catalysts using a spatial confinement strategy, achieving an optimal dFe–Rh that enhances the catalyst's intrinsic ORR activity. The catalyst exhibits a half-wave potential of 0.91 V, surpassing that of commercial Pt/C (0.86 V). The study emphasizes the critical role of determining the site-distance effect in dissimilar metal atoms catalysts for the design of efficient catalyst systems. Density functional theory (DFT) calculations and experimental characterizations, including X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), support the findings. The results show that the site-distance effect influences the interaction strength between Fe and Rh atoms, which is crucial for the ORR process. The study underscores the importance of precise control over atomic distances in SACs to achieve high-performance electrocatalysts for practical applications. The findings contribute to the understanding of how atomic distance regulation can enhance the catalytic activity of SACs, offering a promising strategy for the development of efficient and cost-effective catalysts for ORR.