In this work, an aqueous (2-hydroxyethyl)-trimethyl-ammonium (S)-2-pyrrolidinecarboxylic acid salt ([Cho][Pro]) + K2CO3 solution was studied as a novel absorbent for CO2 capture, and the kinetics and mechanism of the CO2 absorption/desorption process were systematically investigated. Adding [Cho][Pro] to the aqueous K2CO3 solution improved the absorption rate of the solution during the initial stage, and the apparent CO2 absorption rate increased as the concentration of [Cho][Pro] increased. Meanwhile, equilibrium was reached faster when [Cho][Pro] was added, and a tradeoff was noticed between the apparent absorption rate constant and equilibrium absorption amount. The desorption rates of the CO2-rich aqueous [Cho][Pro] + K2CO3 solutions were higher than that of the aqueous [Cho][Pro] solution at 363.15 K, and the highest apparent desorption rate constant was achieved for the aqueous 20 wt.% [Cho][Pro] + 10 wt.% K2CO3 solution. A further study on the aqueous 20 wt.% [Cho][Pro] + 10 wt.% K2CO3 solution indicated that the desorption amount increased with the increase in the temperature from 348.15 to 365.15 K. Moreover, with further increase in temperature, the desorption amount exhibited a lower increasing rate when temperature was higher than 361.15 K. The 20 wt.% [Cho][Pro] + 10 wt.% K2CO3 absorbent exhibited more stable regeneration performance after 7 cycles and lower desorption activation energy than the aqueous 30 wt.% monoethanolamine (MEA) and 30 wt.% [Cho][Pro] solutions as well as higher working capacity compared to the aqueous 30 wt.% [Cho][Pro] solution.