Bipolar membrane electrodialysis is applied to CO2 recovery from alkaline carbonate solution. CO2 in flue gas is captured by an alkaline hydroxide absorbing solution to form an alkaline carbonate solution. The captured CO2 is recovered from the alkaline carbonate solution via bipolar membrane electrodialysis, and the alkaline solution is regenerated simultaneously. To reduce the power requirement for CO2 recovery, this study considers optimal design and operation. Three membrane arrangements were compared, and the results indicate the membrane arrangement comprising a bipolar membrane and cation exchange membrane is the most energy saving. With further optimization of operation conditions, the minimum power requirement for CO2 recovery was reduced to 2.1 MJ/kg-CO2 (or 2.1 GJ/t-CO2). (C) 2009 American Institute of Chemical Engineers AIChE J, 55: 3286-3293, 2009