The oxygen reduction reaction (ORR) suffers from inherent kinetic limitations arising from the competitive adsorption behavior of *OOH intermediates and their divergent conversion pathways toward either the 4e⁻-dominant route or the 2e⁻-peroxide byproduct. Conventional single-component catalysts fundamentally lack temporal-spatial control to simultaneously accelerate O─O bond cleavage while suppressing *H2O2 desorption. To overcome this kinetic dilemma, herein, we propose a dynamically dual-center coupled synergistic (DCCS) catalytic mechanism enabled by precisely engineered PdRh─Pt nanosheet binary-component interfaces. Multidimensional in situ synchrotron radiation spectroscopy and theoretical studies reveal that the activated 4e⁻ pathway primarily occurs at PdRh sites. Additionally, Pt centers selectively reduce *OOH to *O and *H2O2, whereas neighboring PdRh sites facilitate ultrafast *H2O2 migration and dissociation, effectively complementing the 4e⁻-dominant pathway. Hence, the DCCS catalysis redirects traditionally divergent product pathways toward a singular target product. This interfacial kinetic synergy achieves ultrahigh 4e⁻ kinetics, demonstrated by a six-fold increase of turnover frequency compared to that of commercial Pt/C. Moreover, the derived rechargeable Zn‒air batteries demonstrate exceptional stability over 200 h, establishing a new design principle for breaking kinetics trade-offs in heterogeneous catalysis through molecularly scheduling reaction pathways.
