The solubility of tri-iso-amyl phosphate (TiAP) in supercritical carbon dioxide (SCCO2) was determined at 313-333 K with pressure ranging from 10 to 25 MPa. The solubility data of TiAP in SCCO2 medium were correlated using four semi-empirical models. Selective extraction of uranium from simulated dissolver solution was demonstrated using SCCO2 modified with TiAP. The extraction efficiency of uranium was found to be 95 +/- 5%. The influence of temperature, pressure and acidity on the extraction of uranium was studied. An attempt was made to explain the plausible extraction mechanism.