A multifunctional nano-heterostructured electrocatalyst of transition metal/metal oxide (nickel/nickel oxide) embedded on nitrogen-doped graphene is reported. The hybrid composite of N-doped graphene nanosheets with a high atomic percentage of nitrogen (8.2 at%) and embedded with highly distributed nickel/nickel oxide nanoparticles inside the graphene layers is synthesized by a one pot thermal annealing process. The resultant composite demonstrates excellent electrocatalytic activity utilizing the superior electrocatalytic properties of nickel/nickel oxide nanoparticles supported on nitrogen-doped graphene. The hybrid exhibits efficient oxygen reduction reaction (ORR) properties comparable with state-of-the-art electrode Pt/C with a four-electron transfer pathway and superior oxygen evolution reaction (OER) compared to the state-of-the-art electrode for the OER, Ru/C. Alternatively, this composite acts as an excellent electrode material for the hydrogen evolution reaction (HER) both in acidic and alkaline media. Nevertheless, this composite facilitates the hydrogen peroxide oxidation reaction (HPOR) in the presence of hydrogen peroxide, which is crucial for developing reversible fuel cells and fuel cells with liquid oxidant.