Aniline was chemically bonded to the surface of graphene oxide (GO) via a nucleophilic ring-opening reaction. The aniline-bonded GO was then reduced to reduced graphene oxide (RGO) in the presence of multi-walled carbon nanotubes (MWCNTs), which could prevent the RGO from aggregating. The bonded aniline was further responsible for the grafting of polyaniline (PANI) onto the surface of RGO via chemical oxidative polymerization of aniline, and the resultant PANI–RGO/MWCNT ternary nanocomposite could be used as a supercapacitor electrode with high performance.