In response to the worldwide energy shortage and environmental pollution, the development of energy storage devices with higher efficiency and sustainability has become a common goal among scientists in various countries. Supercapacitors promise to be a new class of electrochemical capacitors that are lightweight, eco-friendly and superior performance. Meanwhile, graphene and carbon nanotubes (CNTs) as the most widespread carbon nanomaterials are an attractive solution for energy storage devices due to their unique properties such as excellent electronic conductivity and activated surface area, high mechanical strength and chemical stability. The agglomeration appears among carbon nanomaterials, which lead to the lower surface area and slower electron transport rate and therefore unsatisfactory capacitive performance. Much effort has gone into preventing the accumulation of carbon based materials, such as compositing conductive polymers with them. Polypyrrole (PPy) is one of the important conducting polymers and has been extensively studied because of its ease of fabrication, high conductivity, good biocompatibility, and low cost. In this work, a kind of novel highly dispersed PPy is firstly designed for decoration onto the surface of pristine multiwalled CNTs, which facilely synthesize a CNTs/PPy core/shell composite via π-π interaction. The decorative PPy shell could prevent the aggregation of CNTs by electrostatic repulsive interaction between them and lead to a high dispersibility of the prepared composite, which could effectively insert into the lamellar structure of graphene, resulting in a high active surface area and capacitive performance of the prepared composite. Keywords: Polypyrrole; Carbon materials; Dispersion; Capacitors