A polar version of the group contribution PC-SAFT equation of state (GC-PPC-SAFT; Tamouza et al., 2004; NguyenHuynh et al., 2008) combined with a method for correlation/prediction of binary interaction parameters k(ij) (NguyenHuynh et al., 2008) is here applied to model vapor-liquid, liquid-liquid and vapor-liquid-liquid phase equilibria of CO2 + alkanol mixtures simultaneously. A cross-association interaction between CO2 and alkanol had to be taken into account to model/predict the mixtures equilibria accurately. The cross-association parameters were evaluated using the so-called CR1 mixing rules supported by ab initio computations. Extensive prediction tests on CO2 + alkanol mixtures involving linear and branched alkanols are carried out. The results obtained showed that in most cases, the correlation and prediction calculations are qualitatively and quantitatively satisfactory: the overall deviations on liquid phase and vapor phase are respectively Delta X = 3-4% and Delta Y = 1-2%. (C) 2014 Elsevier B.V. All rights reserved.