Vapor-liquid equilibria were measured for binary systems including carbon dioxide and free fatty acids such as oleic and linoleic acid, triglycerides as triolein or vegetable oils as sunflower oil, and modelled by the Group Contribution Equation of State (GC-EoS). Binary group parameters used in the calculation and prediction of CO2-triglycerides systems were obtained from the literature but in the case of CO2-free fatty acids, binary group parameters were adjusted through a parameterization strategy. At the end, a unique set of parameters could be established to model systems of vegetable oils at high pressures in the presence of CO2. Moreover, a strategy to calculate the two-phase region in a ternary diagram was also studied. The good correspondence between theoretical and experimental results suggests that the strategy and the set of binary group parameters proposed in this work can be reliable predictive tools for using GC-EoS to describe systems involving vegetable oils with a composition based mainly in free fatty acids and triglycerides, such as those which can be encountered, for example, in oil deacidification processes using supercritical CO2. (C) 2010 Elsevier B.V. All rights reserved.