Phase transfer of metal-organic frameworks is highly desired in many areas, which remains a challenge. Herein, we present for the first time a CO2-driven reversible transfer of amine-functionalized ZIF-90 between organics and water. A mechanistic study showed that the switching is ascribed to the reversible generation of hydrophilic ammonium salts from the reaction of CO2 with the amines on ZIF-90. This unique system has been used for the coupling of trans-esterification reactions, product separation and component recycling for green sustainable processes. This work opens up a new avenue for performing reactions effectively with an easy separation process.