This paper provides the first comprehensive review of the major research progress on this technology. To date such research has focused on two main areas: sorbent development and process development. In the case of sorbent development, pure sodium carbonate and potassium carbonate were tested directly. More recent research has concentrated on using supported sorbents which provide the necessary attrition resistance for use with fluidized-bed or transport reactors. Research on sorbent development has included an examination of the physical properties, carbonation and regeneration reaction behavior, reaction kinetic behavior, and multi-cycle behavior of these alkali metal-based sorbents. By contrast, process development activities have focused on solving the many unique challenges associated with post-combustion CO2 capture using alkali metal-based sorbents. The research on process development included exploration of the effects of operation conditions such as reaction temperature, gas composition, operation pressure, and gas impurities on CO2 capture behavior, continuous operation of the CO2 capture process, and economic evaluation of this process. Finally, this paper discusses the research challenges and opportunities that exist with this technology.