Zn-containing room temperature ionic liquids (Zn-RTILs), prepared from the reactions of ZnBr2 with 1-alkyl-3-methylimidazolium dialkyphosphates ([RMIm][R-2 PO4]). were highly active for the coupling reactions of CO2 with epoxides, producing corresponding cyclic carbonates in high yields. FAB-mass spectral and computational results suggest that [ZnBr(R2PO4)(2)](-) could be an active species for the coupling reaction. Decomposition of cyclic carbonates into epoxides and CO2 during the product recovery process via vacuum distillation was almost negligible even in the presence of a Zn-RTIL up to 130 degrees C. (C) 2011 Elsevier B.V. All rights reserved.