Recently core/shell nanostructures including nanotubes, nanowires, and nanofibers have a considerable attension because multiple or enhanced functionality can be obtained by the synergistic effect of different materials in the formation of a core/shell structure. In this work, porous carbon/carbon core/shell carbon electrode (P-C/C-CE) composed of core graphene and disordered shells were prepared to obtain a new type of carbon electrode materials. The disordered carbon shells were prepared by coating of polyaniline onto the graphene by in-situ polymerization in the presence of nano-sized silica and subsequent carbonization at 850°C. After carbonization, P-C/C-CE showed the hollow structure and crystallinity. In addition, P-C/C-CE exhibited superior electrochemical performance compared to graphene and graphene/PANI composites, which was attributed to the high surface area of P-C/C-CE and the presence of nitrogen groups formed onto carbon electrode after the carbonization of shell polyaniline.