CO2capturewithionicliquids(ILs)hasattractedmanyattentions,andmostworksfocusedonabsorptionabilityatambienttemperatures,whileseldomresearchwasconcernedatelevatedtemperatures.ThisnotonlylimitstheCO2absorptionapplicationatelevatedtemperature,butalsothedeterminationoftheoperationconditionoftheCO2desorptiongenerallyoccurringathighertemperature.ThisworkmainlyreportedCO2solubilitiesinILsatelevatedtemperaturesandrelatedpropertieswerealsoprovided.1-alkyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide([CnMIm][Tf2N])ILswereselectedasphysicalabsorbentsforCO2captureinthisworkduetotheirrelativehigherCO2absorptioncapacitiesandgoodthermalstabilities.Thelong-termstabilitytestsshowedthat[CnMIm][Tf2N]isthermallystableat393.15Kforlongtime.CO2solubilitiesin[CnMIm][Tf2N]weresystematicallydeterminedattemperaturesfrom353.15Kto393.15K.ItdemonstratedthatCO2solubilityobviouslyincreaseswiththeincreaseofpressurewhileslightlydecreaseswithincreaseoftemperature.Asthelengthofalkylchainonthecationincreases,CO2solubilityinILsincreases.Additionally,thethermodynamicpropertiesincludingtheGibbsfreeenergy,enthalpy,andentropyofCO2werealsocalculated.