3D graphene-based electrode catalysts have intrigued tremendous research in energy conversion and storage systems not only for the intrinsic properties of graphene, but also due to its high active density for the oxygen electrode reaction with efficient mass and electron transports. In this work, we try to electronically tailor 3D nitrogen-doped graphene (NG) using alumina (Al), and obtain the flower-like structure with a high Brunauer Emmett Teller (BET) surface area and abundant active sites, as a result, pure cobalt nanoparticles are easily confined. Physical characterizations confirm that this natural tuning of graphene by Al causes the increasing of surface defects, as a result, the physicochemical stability of Al and graphene is improved, and vice versa, consequently, the co-modification of Al and Co induce outstanding oxygen reduction reaction (ORR) performance including distinct onset potential, large diffusion limiting current density, kinetic current density and good stability, which are comparable with those of 20 wt% Pt/C in both alkaline and acidic media; in addition, the fabricated composite also delivers prior oxygen evolution reaction activity, superior to the benchmark RuO2. This hybrid herein exhibits a combined ORR and OER potential gap of 0.745 V, rivaling state-of-the-art bifunctional oxygen electrode catalysts. (C) 2017 Elsevier B.V. All rights reserved.