A Janus TaO/TaN heterojunction hybrid with graphene exhibited excellent activity, selectivity and durability for the 2e- oxygen reduction reaction (ORR), compared to TaON@Gr, due to the optimized O2 adsorption and favored *OOH binding in the Janus TaO/TaN heterojunction. This provides a new approach for the structural design of high-performance 2e- ORR catalysts.