A novel electrochemically exfoliated graphene-molybdophosphoric acid nanohybride (EG-MoPA) was prepared via a simple method. Both scanning electron (SEM) and atomic force microscopy (AFM) results show that MoPA clusters are attached to the surfaces of graphene sheets. By changing the mass ratio of EG-MoPA, the morphology of nanohybrid itself can be significantly modulated, from mostly flat graphene like structure at low amount of MoPA to very uneven, wavy surfaces when MoPA is present in higher concentration. The Raman and Fourier transform infra red (FTIR) spectra in conjunction with electrochemical results indicate that strong interaction exists between the components of nanohybride based on charge transfer and electrostatic interaction of graphene sheets and MoPA. The electrochemical performances are improved by synergetic effect of reversible redox properties of MoPA and the double layer capacitance of a high-surface area of the obtained nanohybrides. The higher current capability of EG was achieved by anchoring the small MoPA concentration on the graphene support. The strong bonding of EG with the MoPA prevents acid to dissolve in the electrolyte upon cycling, enabling the stable capacitance behaviour of the low-doped EG sample. The capacitance for the EG doped with the high amount of MoPA was found to be much larger than for EG. However, the obtained capacitance decreases at the beginning of cycling due to the dissolution of excessive amount of surface MoPA, weakly bonded to the graphene support.