The rational design of non-noble metal-based electrocatalysts for an efficient oxygen reduction reaction (ORR) is an important research topic to promote the advancement of aluminum−air batteries. In this work, heterostructural Co/MnO nanoparticles encapsulated in a N-doped carbon electrocatalyst were prepared via one-step pyrolysis utilizing different reduction potentials of Co and Mn ions, and the heterointerface between the two phases was confirmed. The prepared catalyst displays Pt/C competitive ORR performance because of the interfacial synergy of a Co/MnO Mott−Schottky (M−S) heterostructure, which leads to boosted conductivity, formation of an M−S barrier, and a reduced oxygen reduction energy barrier for excited electrons. Furthermore, the Co/MnO-based aluminum−air battery displays good discharge performance, demonstrating good feasibility for practical application.