In this communication, the synthesis, characterization, and properties of highly conductive core-shell nanocomposites of poly(N-vinylcarbazole) (PNVC)-polypyrrole (PPY) copolymers with multi-walled carbon nanotubes (MWCNTs) are described. A unique free-radical coupling reaction between PNVC and PPY cation radicals in chloroform solvent, using feric chloride as an oxidant, in the presence of suspended MWCNTs in the reaction medium, was used for the synthesis of nanocomposite. Field-emission scanning and transmission electron microscopy studies showed the formation of the core-shell nanocomposite. Raman spectrocopy results as well as thermogravimetric analysis supported the electron microscopic observations. The resulting PNVC-PPY copolymer-coated MWCNTs showed an unprecedentedly increased value of direct electrical conductivity (bulk) compared to the conductivity of all samples even with pure MWCNTs.