AbstractN‐Vinylcarbazole (NVC) is polymerised in the presence of pyridine at 60°C by using azodiisobutyronitrile (AIBN) and benzoyl peroxide (Bz2O2) as initiators and the results are compared with those obtained when benzene is used as the solvent. In the AIBN‐initiated system using pyridine as the solvent the rates of polymerisation follow an usual linear relationship with respect to monomer concentration and a square root dependence with respect to the initiator concentration. In the Bz2O2‐initiated system, however, deviations from these ideal behaviours are observed when benzene and pyridine, respectively, are used as the solvent. Initiation occurs through the complexation of the monomer with Bz2O2and degradative transfer is thought to be mainly responsible for this unusual kinetic beh