The hydrogen bond donor-promoted fixation of CO(2) and epoxides into cyclic carbonates was investigated through experimental and density functional theory studies. A highly effective homogeneous system of 1,2-benzenediol-tetrabutyl ammonium bromide (TBAB) and heterogeneous poly-ionic liquids were developed for the fixation of CO(2) into cyclic carbonates via hydrogen bond activation, based on the understanding of the reaction mechanism and catalyst design. The work hence provides a molecular level understanding of the reaction process and forms the basis for the rational design of catalytic systems for the fixation of CO(2) into useful organic compounds.