Supported monoethanolamine (MEA) sorbents are promising materials for CO2 separation due to their low energy demands. Like any other CO2 separation technologies, CO2 desorption from supported MEA sorbents is the most energy-expensive step in the overall CO2 separation process. The presence of water during CO2 desorption process leads to a significant increase in energy consumption. Therefore, CO2 desorption in the absence of water is an important method to reduce energy consumption of CO2 separation using supported MEA, which is determined by several major factors, including desorption kinetics. However, study on CO2 desorption kinetics of supported MEA is lacking. This research was designed to make progress in this area. The CO2 desorption kinetic model of TiO2-supported MEA is experimentally derived with the data collected within water-free desorption environment and theoretically proved by pseudo-steady state theory. The Avrami-Erofeyev mechanism controls the CO2 desorption process, which is first order with respect to [RNH3 +RNHCOO-] or RNH3+ or RNHCOO-. The activation energy of the CO2 desorption process is 80.79 kJ/mol. The kinetic characteristics of the CO2 desorption are much superior to those associated with aqueous MEA based CO2 separation. The energy saving due to the use of supported MEA for CO2 separation not only results from avoiding the use of water, with its high specific-heat capacity and high vaporization enthalpy, but also from the favorable desorption kinetics of the supported MEA based CO2 separation.