The phase behaviors of toluene/polycyclic aromatic hydrocarbon mixture systems were investigated with a continuous-flow type apparatus at 573.2, 598.2, 623.2 and 648.2 K, while the pressure changed from 1 to 5MPa. The pseudo-binary phase behaviors were predicted with the Peng-Robinson equation of state with interaction parameters between toluene and pseudo-components considered. The phase diagrams of the system have been classified following the category of phase boundary-diagram models. The extraction selectivity and efficiency of toluene as a solvent was discussed by comparing with that of hexane. The prediction model. for selectivity was also suggested.