A new experimental method has been developed for measuring the equilibrium solubility of heavy solutes in supercritical CO2. The micro-SFE (supercritical-fluid extraction) is coupled to supercritical-fluid chromatography (SFC), both operating under the same temperature, pressure, and CO2 flowrate, Naphthalene, biphenyl, and phenanthrene are chosen to verify the method. The isobaric solubilities of the solutes in the temperature range of 308-338 K and pressure from 8.0 MPa to 12.0 MPa are determined, The experimental data are in agreement with literature values and exhibit some characteristics of solid-supercritical-fluid binary system phase equilibrium in the near critical region of solvent.