To extend the application of the COSMO‐SAC model to phase‐equilibrium calculations of polymer solutions, a new strategy for estimating the charge‐density profile, the cavity volume and the cavity surface area of polymer molecules is proposed by finding reasonable parameters for the corresponding repeating structure units. The molecular parameters for polymers are obtained by summing up the corresponding COSMO calculated values of the repeating units calculated by the algorithms of DMol3 (a density functional theory) or MOPAC (a semi‐empirical method). Combining with the COSMO‐SAC model, the activities and equilibrium pressures for several typical polymer solutions are satisfactorily predicted indicating that the proposed method can be used for the prediction of vapor–liquid equilibrium of polymer solutions. It was also found that both DMol3 and MOPAC can be used though the results obtained from them are slightly different. The results in this paper show that the method proposed has the potential to predict other phase‐equilibrium properties of polymer systems. © 2010 American Institute of Chemical Engineers AIChE J, 2010