Multi-walled carbon nanotubes (MWCNTs)-core/thiophene polymer-sheath composite nanocables were synthesized by chemical oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) with oxidant (FeCl3) in the presence of cationic surfactant, deceyltrimethyl ammonium bromide (DTAB). In the polymerization process, DTAB surfactant molecules were adsorbed on the surface of MWCNTs and forms MWCNTs-DTAB soft template. Upon the addition of EDOT and oxidant, the polymerization take place on the surface of MWCNTs and PEDOT is gradually deposited on the surface of MWCNTs. The resulting MWCNTs-PEDOT nanocomposites have the nanocable structure. Nanocomposites were characterized by HRTEM, FE-SEM, XRD, XPS, TGA, FTIR and PL, respectively. The pi-pi interactions between PEDOT and MWCNTs enhancing the thermal and electrical properties of the nanocomposites with loading of MWCNTs. The temperature dependence conductivity measurements show that the conductivity of the nanocomposite decrease with a decrease of temperature, and conductivity-temperature relationship is well fit by the quasi-one dimensional variable range hopping mode. The mechanism for the formation of composite nanocables was explained on the basis of self-assembly of micelles. The reported self-assembly strategy for the synthesis of PEDOT-coated MWCNTs in micellar medium is a rapid, versatile, potentially scalable, stable, and making it useful for further exploitation in a varies types of applications. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48:1477-1484,2010