A novel strategy has been developed to prepare hollow structured Nafion-modified-graphene/polyaniline (NGP) composites via interfacial assembly polymerization between an aqueous phase containing oxidant and an organic phase containing aniline monomers and Nafion-modified graphene. Fourier transform infrared (FTIR), Ultraviolet-visible (UV-vis) and X-ray diffraction (XRD) analyses confirmed the generation of polyaniline (PANI) on graphene during the interfacial polymerization. The morphological evolution of the product had been investigated by scanning electron microscopy (SEM) with respect to the reaction time, based on which a conceivable interpretation of the growth mechanism of the sphere architectures with composite component were given. The as-prepared hollow structured composites showed a good rate capability as electrode material for supercapacitor, and the as-designed interfacial assembly preparation strategy for such composites may provide a generic guideline in developing other graphene-base composite hollow spheres with different compositions. (C) 2014 Elsevier Ltd. All rights reserved.