PGM-free (platinum group metal) electrocatalysts are intensively investigated and used as low-cost catalysts for the oxygen reduction reaction (ORR) in the field of fuel cells, but further studying their performance improvement methods and actual reaction mechanism is still a big a challenge. In this work, a novel eletrocatalyst containing atomically dispersed Mn/Fe single atoms (SAs) and Fe nanoparticles (NPs) on N-doped carbonaceous (nanosheet/nanotube hybrids) is fabricated via a simple pyrolysis method. This high-activity ORR electrocatalyst has higher half-wave potential (E1/2 = 0.91 V) and superior long-term durability in alkaline solutions and outperforms Pt/C catalysts, which can be ascribed to the synergetic interaction between Mn/Fe SAs and Fe-NPs. FeNPs/MnFeSAs-NC-25 has stronger reactant adsorption ability and a lower dissociation energy barrier than FeNPs/FeSAs-NC, which is conducive to breaking the O-O bond and accelerating ORR kinetics. This work presents a method to synthesize carbon-based electrocatalysts with high ORR activity and stability and shows that a variety of active sites encapsulated in N-doped carbonaceous materials can be a class of competitive candidates for PGM-free electrocatalysts.