A new kind of urethane-based poly(ionic liquid)s (Pas) was synthesized by the addition of diisocyanate to a difunctional polyol and diol mixture, which then went through an exchange reaction with the ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). Different PILs were attained by means of the addition of diethanolamine, hydrazine and ethylenediamine as chain extenders, and in the course of the variation of the polyol' molecular weight. Such materials were used as catalysts in the cycloaddition of CO2 to epoxide and obtain cyclic carbonate. The effects that the variations carried out with the Pas composition is as catalysts in its performance, as the catalytic reaction parameters (temperature, pressure & time) were investigated just as well. The results demonstrate that the variation of PILs compositions influence their physical and thermal properties, along with its catalytic activity. A higher CO2 conversion was obtained by extending PIL with ethylenediamine (PUEA BMIM) at mild conditions of 25 bar, 110 C and 6h, which can be easily separated and recycled without the loss of catalytic activity. (C) 2014 Elsevier B.V. All rights reserved.