An enzyme-catalyzed desorption process for releasing CO2 gas from an ion-rich solution containing bicarbonate ions includes providing carbonic anhydrase in the ion-rich solution such that in a desorption unit the carbonic anhydrase is allowed to flow with the ion-rich solution while promoting conversion of the bicarbonate ions into CO2 gas and generating an ion-depleted solution and releasing the CO2 gas and the ion-depleted solution from the desorption unit. A CO2 capture process includes contacting a CO2-containing gas with a solution in an absorption unit, to convert CO2 into ions; feeding an ion-rich solution to a desorption unit wherein carbonic anhydrase is present within the ion-rich solution to generate an ion-depleted solution and, preferably, recycling the ion-depleted solution. Methods of decreasing the CO2 desorption temperature in a desorption unit, decreasing the CO2 desorption reactor size, and decreasing the CO2 desorption energy input in a desorption unit, are also described.