Chemical fixation of CO2 into useful organic compounds has been attracting much attention from the viewpoint of CO2 emission reduction and energy structure reformation. A useful and widely investigated chemical utilization of CO2 is the cycloaddition of CO2 to epoxides for the synthesis of cyclic carbonates. Efforts have been paid to the design and preparation of various catalyst systems that are active and selective to the production of the desired products under mild conditions and in green processes. This article is to review the current state of the catalyst development and the experimental and theoretical analysis of reaction mechanism for the cyclic carbonate synthesis from epoxides, one of currently important reactions involving CO2 as a reactant with 100% atom economy. Particular attention is given to the catalysis of multifunctional catalyst systems such as metal- and hydrogen-bond donor (HBD)-based catalysts.