Aqueous carbonation of Ca(OH)2 is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO2 in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO2 with Ca(OH)2. The use of the IL increased the solubility of CO2 in the aqueous environment and enhanced the transport of the reactive species (Ca2+ and CO32-) and products. The presence of the IL also avoided the formation of the CaCO3 protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time.