A triangular phase diagram of the polystyrene/styrene/ethylene-vinyl-acetate (PS/SM/EVA) system is established to account for the phase change during polymerization of SM. The phase behaviors for EVA and PS domains in the SM polymerization system are also studied by an optical microscope (OM) and a photometer. Both EVA and PS dissolve in SM quite easily, but PS and EVA are immiscible. Hence, the exclusion of PS from the EVA phase domain results during the polymerization. That is, the polymer solution will be phase-separated at the initial stage of polymerization. Additionally. EVA phase inversion occurs as the conversion of SM increases to 15%, at which the volume ratio of EVA/PS is approximately unity. Monitoring the light transmittance level of EVA/PS/SM solution during polymerization, the EVA phase proves to have been completely inverted to the dispersed phase when the SM conversion reaches 20%.