Switchable polarity ionic liquids (SWILs) with low moisture sensitivity were successfully synthesized from organic amidine/fluoroalcohol and guanidine/fluoroalcohol via proton transfer reaction. The ionic liquids showed low polarity and could be converted into high polarity fluoroalkylcarbonate ILs upon the treatment with CO2 under mild conditions. Their high polarity state could also readily be reverted to the low polarity state by the removal of CO2 with heating. Changes in the structures and physical properties resulting from the change from low polarity to high polarity were confirmed by NMR spectroscopy, FTIR spectrophotometry, UV-vis spectroscopy, and conductivity and miscibility measurements. These SWILs have potential applications in solute separation and solvent recovery. (C) 2013 Elsevier Ltd. All rights reserved.