N-vinylcarbazole (NVC) was polymerized in bulk or in toluene in presence of multiwalled carbon nanotube (MWCNT) without any extraneous catalyst. The formation of polyN-vinylcarbazole (PNVC) was endorsed by striking agreement of FTIR, fluorescence and UV-visible spectroscopic, thermogravimetric stability, differential scanning calorimetry, and dielectric characteristics of this polymer with the corresponding literature data for authentic PNVC samples prepared by free radical or carbocationic initiation. The polymerization was supposed to be initiated by a single electron transfer between N lone pair of NVC and the electron deficient MWCNT moieties. While PNVC homopolymer is non-conducting (10(-12) to 10(-16) S / cm), a composite of PNVC with MWCNT isolated from the polymerization system showed high dc conductivity varying from 1.3 to 33 S / cm depending upon the extent of MWCNT loading in the composite. (c) 2007 Wiley Periodicals, Inc.