Synergistic catalysis opens up a new venue to improve the comprehensive application of the catalyst. Herein, a composite catalyst (Mo-Pd@N-C) consisting of the N-doped carbon derived from pyrolysis of spherical polypyrrole and MoPd nanoparticles (NPs) was constructed to emphasize the strong metal–support interaction for robust oxygen reduction reaction (ORR). The enhanced anchoring between the MoPd NPs and the substrate, and the N-species formed on the carbon matrix make the Mo-Pd@N-C deliver excellent performance with a half-wave potential of 0.945 V (vs. reversible hydrogen electrode (RHE)) for ORR, superior than that of commercial Pt/C (0.86 V). More importantly, it shows a negligible half-wave potential decline (< 5 mV) and only ~ 20% of mass activity (MA) attenuation after 30,000 cycles stability test, obviously better than those of Pt/C (~ 70% of MA attenuation and ~ 30 mV of half-wave potential decline after only 15,000 cycles). This work highlights a novel synergistic method to prolong the life and improve the commercial prospects of the catalysts.