This work presents an approach to accurately modeling the mutual solubilities and multiphase behavior of aqueous systems. For this purpose, a new PC-SAFT parameters set for water was proposed and temperature-dependent binary interaction parameters, k(ij)(T) were determined by fitting to the mutual solubilities data of water/n-hexane and water/benzene mixtures. These k(ij)(T) have been used to predict the mutual solubility and multiphase equilibria of similar mixtures for an extended temperature range up to 473 K. Very good agreement between predicted results and available experimental data has been obtained, including the description of the minimum of hydrocarbon solubility in water as a function of temperature. The model's overall average relative deviations from experimental data were 19.9% and 18.1% for the solubility of water in organic phase and of hydrocarbons in aqueous phase, respectively. To test the model's capabilities, the parameters were used to predict multiphase behavior for water-alcohol-hydrocarbon ternary systems and gave good results compared with experimental data. (C) 2018 Elsevier B.V. All rights reserved.