Ammonium-based ionic liquid monomers and their corresponding polymers [poly(ionic liquid)s] are synthesized and characterized for CO2 sorption. The polymers have much higher CO2 sorption capacities than the room-temperature ionic liquids and imidazolium-based poly(ionic liquid)s. For example, P[VBTMA][PF6] with polystyrene backbone has a CO2 sorption capacity of 10.67 mol%. The CO2 Sorption is selective over N-2 and O-2. The effects of cation, backbone, substituent, anion and crosslinking on CO2 sorption are discussed. The sorption mechanism study indicates that CO2 sorption by the poly(ionic liquid)s is a bulk and surface phenomenon. (c) 2005 Elsevier Ltd. All rights reserved.