A series of novel functionalized phosphonium-based ionic liquids (FPBILs) were synthesized by a simple method, and first evaluated as catalysts for the synthesis of cyclic carbonates through the cycloaddition of CO2 to epoxides in the absence of co-catalyst and solvent. The FPBILs perform well in the cycloaddition reaction, especially the carboxyl-functionalized one. Over [Ph3PC2H4COOH]Br, the yield of propylene carbonate is 97.3% (TOF = 64.9 h(-1)) at 130 degrees C and 2.5 MPa in 3 h. The synergistic effects of polarization induced by hydrogen bonding and nucleophilic attack of Br- anion account for the excellent performance. Furthermore, the FPBILs with moderate methylene chain length show superior catalytic activity. It is because they have both strong acidity and weak electrostatic interaction between phosphonium cation and halide anion. The strong acidity facilitates the ring-opening of epoxyl, and the weak electrostatic interaction enhances the nucleophilic attack capability of Br-. It is envisaged that the metal- and solvent-free process has high potential for the catalytic conversion of CO2 into value-added chemicals. (C) 2013 Elsevier B.V. All rights reserved.