Abstract Many commercially important mixtures contain complex polymers, e.g. paints and coatings. If a good thermodynamic description can be given of these systems it is possible to develop paints, which possess a certain set of properties and at the same time meet some basic requirement as, e.g. regarding the content of organic solvents. This work presents an investigation of the three polymer models Entropic-FV (EFV), UNIFAC-FV (UFV) and GC-Flory (GCF) for their capability of predicting solvent activity coefficients in binary systems containing complex polymers. It is possible to obtain good predictions at finite concentrations and satisfactory predictions at infinite dilution, particularly with the EFV model. The investigation shows that EFV is the most robust and stable of the models, which indicates that it is the most well suited model for further development of methods for predicting the miscibility behavior of paints and related systems.