The cobalt-mediated radical polymerization (CMRP) of 1-vinyl-3-ethylimidazolium bromide (VEtImBr) is described. Polymerizations were performed at 30 degrees C in solution either in dimethylformamide (DMF) or in methanol (MeOH) or in a mixture of both solvents, using a preformed alkyl-cobalt(III) adduct, CH(3)OC(CH(3))(2)CH(2)-C(CH(3))(CN)-(CH(2)-CHOAc)(<4)-Co(acac)(2), as the mediating agent. Excellent control over molecular weights and dispersities (M(w)/M(n) similar to 1.05-1.06) was achieved in MeOH, with a linear increase of experimental molecular weights with the monomer conversion. Substituting methanol for DMF induced much faster polymerization process, even under quite high diluted conditions: for instance, about 80% monomer conversion was reached in 30 min in DMF, compared to 10 h in MeOH. However, size exclusion chromatography (SEC) traces of PVEtImBr samples synthesized in DMF revealed a side population in the high molecular weight region, presumably due to the occurrence of irreversible coupling reactions of a small proportion of growing chains. Well diblock copolymers featuring both a poly(vinyl acetate) (PVAc) block and a PVEtImBr-based poly(ionic liquid) block, PVAc-b-PVEtImBr, were next obtained by sequential CMRP of VAc and VEtImBr. To this end, a PVAc-Co(acac)(2) was first prepared by CMRP and employed as a macroinitiator for the polymerization of VEtImBr either in methanol or in a mixture of DMF and MeOH (2/1: v/v) at 30 degrees C. Finally, cobalt mediated radical coupling (CMRC) of the aforementioned PVAc-b-PVEtImBr diblock copolymers, Using isoprene as a simple coupling agent, led to unprecedented and structurally well-defined PVAc-b-PVEtImBr-b-PVAc triblock copolymers.