Nanostructured polypyrrole coating was applied on carbon paper via simple dip-coating and electrochemical approach. Hybridization with nanocarbon materials (graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs)) and their effect as an anchoring hybrid layer for the growth of polypyrrole towards improving electrochemical properties are studied. The loading of each component and their ratio were evaluated. Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and Raman spectroscopy were employed to characterize the properties of the coatings. The electrochemical properties were investigated by cyclic voltammetry. The results indicated the electrodeposition of polypyrrole is enhanced by the addition of MWCNTs to the GO layer due to the formation of a hierarchical network. The electrochemical performance of the modified electrode was shown to be highly dependent on the employed ratio, reaching a capacitance value of about 40 mF cm for a carbon paper substrate modified with GO:MWCNT in a ratio of 1:2.5 and PPy layer deposited by cyclic voltammetry for 30 cycles. The contribution to total stored charge was found to be primary from the inner capacitance component of about 95.5% contribution.