Recently, much research has investigated nanocomposites and their properties for the development of energy storage systems. Supercapacitor performance is usually enhanced by the use of porous electrode structures, which produce a larger surface area for reaction. In this work, a biocompatible polymer of starch medium was used to create the porous nanostructure. Two powders, i.e., Nickel molybdate/reduced graphene oxide (NiMoO4-rGO) and Nickel molybdate/nitrogen-doped reduced graphene oxide (NiMoO4-NrGO), were synthesized using the deposition method in a medium containing starch, nickel nitrate salts, sodium molybdate, and graphene oxide powder. In terms of electrochemical performance, the NiMoO4-NrGO electrode displayed a higher specific capacitance, i.e., 932 Fg−1 (466 Cg−1), than the NiMoO4-rGO electrode, i.e., 884 Fg−1 (442 Cg−1), at a current density of 1 Ag−1. In fact, graphene oxide sheets could lose more oxygen groups in the presence of ammonia, resulting in increased electrical conductivity. For the asymmetric supercapacitor of NiMoO4-NrGO//AC, the specific capacitance at 1 Ag−1, energy density, and power density were 101.2 Fg−1 (111.32 Cg−1), 17 Wh kg−1, and 174.4 kW kg−1, respectively. In addition, this supercapacitor material displayed a good cycling stability of over 82%.