Polymer grafting from graphitic carbon materials has been explored for several decades. Currently existing methods mostly employ harsh chemical treatment to generate defect site in graphitic carbon plane, which are used as active site for polymerization of precursors. Unfortunately, the treatment cause serious degradation of chemical structure and material properties. Here, we present a straightforward route for growth of polyaniline chain from nitrogen (N)-sites of carbon nanotubes. N site in the CNT wall initiates the polymerization of aniline monomer, which generates seamless hybrids composed of polyaniline directly grafted onto the CNT walls. The synthesized hybrids show excellent synergistic electrochemical performance, and are employed for electrodes of pseudo-capacitor. This approach offers an efficient way to obtain hybrid system consisting of conducting polymers directly grafted from graphitic dopant sites.