A coupled reaction and solvent extraction process to produce Li2CO3 from LiCl and CO2 is proposed. The aqueous reaction occurs with difficulty and is not spontaneous at 298 K. To ensure the continuous reaction between LiCl and CO2 to produce Li2CO3, it is necessary to remove HCl. Experiments conducted in an open reactor at room-temperature showed that the product sample was pure Li2CO3 with a particle-size distribution in two regions and a larger number of small crystals. The large and small crystals were obtained by radial growth in the free aqueous phase and in water-in-oil structures with growth space constraints, respectively. Factors influencing the particle-size distribution and Li2CO3 morphology were investigated. A short reaction time, large phase ratio (O/A), low-temperature, and surfactant addition (TritonX-100) can increase the number of small particle crystals and reduce the number and volume of large particle crystals. (c) 2013 American Institute of Chemical Engineers AIChE J, 60: 282-288, 2014