In the present work, a highly efficient and excellent electrocatalyst material for bifunctional oxygen reduction/evolution reaction (ORR/OER) was synthesized using the microwave-assisted hydrothermal method. In brief, ultrafine hexagonal cerium oxide (CeO2) nanoparticles were tailored on the layered surface of in situ nitrogen-doped graphene oxide (NGO) sheets. The nanocomposites exhibited a high anodic onset potential of 0.925 V vs. RHE for ORR activity and 1.2 V for OER activity with a very high current density in 0.5 M KOH. The influence of oxygen cluster on Ce3+/Ce4+ ion decoration on outward/inward in situ nitrogen-coupled GO enhanced the physicochemical properties of composites and in turn increased electron transferability. The microwave-assisted hydrothermal coupling technique provides a higher density, active sites on CeO2@NGO composites, and oxygen deficiency structures in ultrafine Ce-O particles and boosts higher charge transferability in the composites. It is believed that the physical states of Ce-N- C, Ce-C=O, and a higher amount of oxygen participation with ceria increase the density of composites that in turn increases the efficiency. N-doped graphene oxide promotes high current conduction and rapid electron transferability while reducing the external transport resistance in oxygen electrocatalysis by sufficient mass transfer through in-built channels. This study may provide insights into the knowledge of Ce-enabled bifunctional activity to guide the design of a robust catalyst for electrochemical performance.