A new class of soluble conductive poly(N-vinylcarbazole) (PVCz) compounds has been developed by oxidative matrix polymerization of N-vinylcarbazole (NVCz) by Ce(IV) in the presence of poly(ethylene glycol) (PEG). PEG was found to be a more suitable matrix with which to obtain a stable homogenous ternary complex solution when compared with poly(acrylic acid) (PAA) and poly(vinyl-pyrrolidone) (PVP). The role of PEG, NVCz and Ce(IV) concentration, order of component addition, the structure of the polymer matrix, molecular weight of polymer and the effect of solvent have been investigated. Obtaining soluble PEG-Ce(III)-PVCz ternary complexes was shown by cyclic voltammetric measurements, and the initial rate of formation NVCz cation radicals as calculated using UV-visible spectrophotometry. Advantageously with these soluble complexes, conductivities could be measured both in solution and in the solid state. (C) 2001 Society of Chemical Industry.