The near-azeotrope mixture of TFE and CO2 is an important concern urging the scientific community to develop new ways for TFE/CO2 separations. In this work, for the first time, Diisopropylamine (DIPA) and Diethanolamine (DEA) are used as solvents for separating a near-azeotropic mixture of CO2 and tetrafluoroethylene (TFE). The complete separation mechanism has been analyzed using ASPEN Plus process simulator. The binary parameters for CO2, TFE, DIPA and DEA have been taken from Cosmotherm software and the pure data parameters have been taken from the literature (NIST). The validation of the processes has been completed by comparing binary parameters with literature and pure parameters with the UNIFAC data. The separation of the near-azeotropic mixture of TFE and CO2 has been investigated where, both solvents can be proposed as good candidates, however DEA is proven better performer than DIPA. In addition, CO2 emissions analysis and Total Annual Cost (TAC) analysis has been performed for the payback period of 3, 5 and 7 years, where DEA proves to be most efficient for TAC while DIPA has less CO2 emissions.