In this paper we report upon the preparation and characterization of electrospun nanofibers of doped polyaniline (PANI)/poly(methyl methacrylate) (PMMA)/amino-functionalized graphene (Am-rGO) by electrospinning technique. The successful functionalization of rGO with amino groups is examined by Fourier transforms infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and Raman microspectrometer. The strong electric field enables the liquid jet to be ejected faster and also contributes to the improved thermal and morphological homogeneity of PANI/PMMA/Am-rGO. This results in a decrease in the average diameter of the produced fibers and shows that these fibers can find promising uses in many applications such as sensors, flexible electronics, etc.