This work proposes an innovative concept for the removal of CO2 from flue gas streams using supported liquid membranes with non-volatile ionic liquids (or solvents), comprising a thermoresistant enzyme that enhances the selective transport of CO2. Membrane stability, CO2 and N-2 permeability and CO2/N-2 ideal selectivity was determined in the membranes developed. The selected liquid phases - the ionic liquid [C4MIM][Tf2N] and the organic solvent PEG - were immobilized in a porous hydrophobic polymeric support. The effect of introducing the carbonic anhydrase enzyme, on the solubility and diffusivity of CO2 and N-2 through these solvents, under controlled water activity conditions, was investigated. These results show that the supported liquid membranes prepared were stable at high temperatures and selective towards CO2 when compared with N-2. Depending on the water activity of the solvents, the presence of enzyme may increase the CO2 solubility coefficient up to 30%, even if a low enzyme concentration is used. These results illustrate the potential of using this approach to further enhance the performance of SLMs impregnated with ionic liquids for capture of CO2. (C) 2012 Elsevier B.V. All rights reserved.