A mixture of Polyvinylpyrrolidone (PVP), graphene and emeraldine base polyaniline (PANi) was electrospun and used as starting materials to prepare a nitrogen-doped carbon nanofiber (N-CNF). Nickel oxide was loaded on the N-CNF to form a nanocomposite which was calcined later at different temperatures. The effect of calcination temperature on the electrocatalytic behavior of the nanocomposite was studied which shows that the nanocomposite calcined at 500 °C was proved to be very high compared to the other calcination temperatures. The stability of catalyst was excellent and its resistance to the adsorption of the intermediates generated from the methanol oxidation was very high.