Phase separations of Poly(4-vinylphenol)(PVPh)/Ethyl Acetate and PVPh/Butyl Acetate solutions were measured using the thermal optical analysis (TOA) method. The experimental phase separation data were correlated with liquid-liquid equilibria relations based on PC-SAFT equation of state. The phase separations of these system showed the behaviors of LCST (lower critical solution temperature)-type. The measured cloud temperatures were lowered with increasing in molecular weights of polymer(PVPh), and cloud temperatures of PVPh/Ethyl Acetate solutions shifted to lower temperature regions, compared to the PVPh/Butyl Acetate solutions. Extents of cross-association between solvent molecule and polymer in the PVPh/Ethyl Acetate solutions were measured using the FT-IR spectrum analysis method, and cross-association parameters of PC-SAFT model were estimated from experimental extents of cross-association. By using the estimated cross-association parameters between PVPh and solvent molecule, binodal and spinodal curves of liquid-liquid equilibria in PVPh/Ethyl Acetate and PVPh/Butyl Acetate solutions were calculated from PC-SAFT equation of state. The calculated binodal curves of these system were shown to be well agreeable with the experimental cloud temperature curves.