The present study reports a new nanocomposite design using surface modified silver nanowires decorated on the surface of polyethyleneimine (PEI), a cationic polymer acting as glue for anchoring nanowires and reduced graphene oxide (rGO). The synthesized nanocomposite was employed as a promising electrode material for immobilization of biomolecules and effective transportation of electron, in enzymatic biofuel cell (EBFCs) application. The synthesized nanocomposite was confirmed by analytical techniques, for instance, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The electrochemical behaviour of the nanobioelectrocatalysts rGO-PEI/Frt/GOx, rGO-PEI/AgNWs/Frt/GOx, and rGO-PEI/Naph-SH/AgNWs/Frt/GOx was determined by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). The maximum current density obtained by the modified bioanode was found to be 19.9 mA cm-2 at the limiting glucose concentration of 50 mM in PBS (pH 7.0) as supporting electrolyte at a scan rate of 100 mVs-1.