Adjusting the selectivity of the oxygen reduction reaction (ORR) is crucial for energy technologies: the four-electron (4e-) transfer enables the operation of fuel cells and metal-air batteries, while the two-electron (2e-) reduction promotes the production of hydrogen peroxide (H2O2). However, achieving precise control over the catalytic ORR pathways remains a significant challenge. In this study, a feasible solution of tailoring differential pyrolysis was adopted to regulate the ORR selectivity of FeMn-based catalysts. Notably, iron (Fe)-doped Mn2O3 nanoparticles loaded on boron (B) and nitrogen (N) co-doped carbon nanosheet (FMO-BNC), prepared by rapid heating (10 °C/min) within the temperature range of 310-400 °C, follows a 2e- transfer pathway, selectively generating H2O2 with a yield of 84.4 %. In contrast, dual-atom FeMn grown on B and N co-doped carbon (SAFM-BNC), synthesized by rapid heating (10 °C/min) in the range of 400-900 °C, facilitates a 4e- transfer route, exhibiting a half-wave potential (E1/2 = 0.87 V) comparable to that of commercial Pt/C. The combination of experimental and simulation results indicates that differential pyrolysis modulates the active sites of the catalyst, optimizing the energetics of intermediates to achieve site-dependent ORR selectivity.