This work describes a thermostable biomimetic membrane system using supported ionic -liquid membranes (SILMs) and an "extremo-enzyme" that enhance the selective transport of CO2 at high temperatures (up to 373 K). The membranes are impregnated with the thermophilic Sulfurihydrogenibium yellowstonense carbonic anhydrase SspCA isozyme and are expected to fill the gap between the thermal stability of biocatalyst and highly membrane performance for CO2 separation processes at high temperatures. Membrane stability, gas permeability and ideal selectivity were determined in the membranes developed. The results obtained show that the SILMs prepared present interesting permeability (P-co2=733.73 barrer) at high temperatures (up to 373 K) and a good transport selectivity towards CO2 against N-2 (alpha(CO2/N2)=35.6). These results illustrate the potential of using this approach to further enhance the performance of enzyme impregnated SILMs for removal of CO2 from flue gas streams.