Hydrogen fuel cells have drawn increasing attention as one of the most promising next-generation power sources for future automotive transportation. Developing efficient, durable, and low-cost electrocatalysts, to accelerate the sluggish oxygen reduction reaction (ORR) kinetics, is urgently needed to advance fuel cell technologies. Herein, we report on metal-organic frameworks-derived nonprecious dual metal single-atom catalysts (SACs) (Zn/Co-N-C), consisting of Co-N4 and Zn-N4 local structures. These catalysts exhibited superior ORR activity with a half-wave potential (E1/2) of 0.938 V versus RHE (reversible hydrogen electrode) and robust stability (ΔE1/2 = -8.5 mV) after 50k electrochemical cycles. Moreover, this remarkable performance was validated under realistic fuel cell working conditions, achieving a record-high peak power density of ∼1 W cm-2 among the reported SACs for alkaline fuel cells. Operando X-ray absorption spectroscopy was conducted to identify the active sites and reveal catalytic mechanistic insights. The results indicated that the Co atom in the Co-N4 structure was the main catalytically active center, where one axial oxygenated species binds to form an Oads-Co-N4 moiety during the ORR. In addition, theoretical studies, based on a potential-dependent microkinetic model and core-level shift calculations, showed good agreement with the experimental results and provided insights into the bonding of oxygen species on Co-N4 centers during the ORR. This work provides a comprehensive mechanistic understanding of the active sites in the Zn/Co-N-C catalysts and will pave the way for the future design and advancement of high-performance single-site electrocatalysts for fuel cells and other energy applications.