In this study, dual-metal atomic pairs of manganese (Mn)-iron (Fe) binuclear sites (BNSs) with two conjoint MnN₄ and FeN₄ moieties (MnFeN₈) anchored onto a graphite-like structure (GLS) (Mn-Fe BNSs/GLS) were constructed. The binuclear MnFeN₈ structure was verified experimentally and theoretically. Magnetic measurements and Gaussian calculations reveal that this unique Mn-Fe BNSs exhibit strong short-range electronic interaction between Mn and Fe sites, which decouples two paired d electrons in Fe sites, thereby transforming Fe sites from an intermediate to a high spin state. The optimal electronic configuration of Fe sites and their binuclear structure facilitate an oxygen reduction reaction (ORR) thermodynamically and dynamically, respectively, endowing Mn-Fe BNSs with improved ORR performance.