The phase and volumetric behaviour of binary mixtures of n-alkanes and n-perfluoroalkanes at subcritical conditions have been studied using the SAFT-VR equation of state. In previous work [C. McCabe, A. Galindo, A. Gil-Villegas, G. Jackson, Predicting the high-pressure phase equilibria of binary mixtures of perfluoro-n-alkanes plus n-alkanes using the SAFT-VR approach, J. Phys. Chem. B 102 (1998) 8060-80691] the SAFT-VR equation was successfully used to predict the phase behaviour of binary mixtures of low molecular weight n-perfluoroalkanes + n-alkanes. A transferable binary interaction parameter was proposed which enabled the accurate prediction of the critical lines for all the systems studied. In this work we focus on the low pressure liquid-liquid immiscibility displayed by binary mixtures of longer chains (C-5-C-8). New transferable binary interaction parameters for these mixtures are proposed, based on the reproduction of the UCST and excess volumes for the n-hexane + n-perfluorohexane system. With these parameters, predictions are then made for the vapour-liquid equilibria (VLE), liquid-liquid equilibria (LLE) and excess volumes of other binary mixtures without any additional fitting to experimental data. The resulting predictions from the SAFT-VR equation are in good agreement with the available experimental data. (c) 2004 Elsevier B.V. All rights reserved.