This paper presents a comprehensive thermodynamic study of binary mixtures formed by 1-butyl-1-methylpyrrolidinium tetracyanoborate ionic liquid and hydrocarbons (n-heptane, benzene, toluene, ethylbenzene), thiophene and alcohols (methanol, ethanol, 1-propanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol and 1-dodecanol). An impact of chemical structure of molecular compounds on their solubility in the ionic liquid and excess enthalpies of mixing is discussed. Furthermore, modelling of the measured properties by using perturbed-chain statistical associating fluid theory (PC-SAFT) is presented. The theory is applied in both correlative and semi-predictive mode involving temperature-dependent binary corrections fitted to infinite dilution activity coefficients. Solubility curves and excess enthalpies are captured by the model with a reasonable accuracy, when semi-predictive strategy is adopted. Moreover, (liquid + liquid) equilibrium phase diagram in ternary system composed of the investigated ionic liquid, thiophene and n-heptane is predicted with PC-SAFT and then the calculations are confronted with available experimental data. The results indicate that the approach proposed can be perceived as an interesting tool for reproducing the thermodynamic behaviour disclosed by such complex systems as those based on ionic liquids. (C) 2015 Elsevier Ltd. All rights reserved.