We report the synthesis of highly ordered N-doped mesoporous carbon/graphene frameworks (N-MCF/N-MGF), which possessed large surface area, high porosity, excellent internal diffusion property, and superior intrinsic conductivity and exhibited promising catalytic properties in both ORR and OER. As a dual catalyst, the N-MGF exhibited overpotential as low as 324 mV for harvesting 10 mA cm-2 OER current density, which was lower than most of previously reported carbon-based materials and were comparable with the benchmarking noble metal oxide catalysts. The catalyst was also durable under both OER and ORR conditions. These results presented a low-cost dual ORR/OER electrocatalyst with high activity and good durability as well as their negligible internal diffusion resistance, which could be potentially utilized and implemented in renewable energy techniques such as metal-air batteries, fuel cells, and water splitting devices.