Based on the electron-donating properties of N-vinyl carbazole and electron-accepting capacity of dichlorobenzene, the first step of the study consisted in the mixing of the two components. As a result, it is formed a charge transfer complex (CTC) able to participate in a polymerization reaction by two types of mechanism. Radical as well as cationic polymerization mechanisms have been highlighted. The proposed kinetic model has been validated by the experimental data. The donor:acceptor ratio and the reaction medium influence the proportion of the two types of polymerization mechanism, as confirmed by the GPC analysis. The CTC has been investigated by UV–VIS.