A good understanding and prediction of the phase equilibrium of the fatty acid methyl ester (FAME) + glycerol + methanol ternary system is needed to design and optimize the separation unit of the biodiesel production process. In this work, new experimental vapor liquid liquid data on the ternary system have been measured at temperatures between 333.15 and 473.15 K. In addition, new data have been gathered on the methanol + glycerol [vapor liquid equilibrium (VLE)] and methanol + methyl oleate (VLE and liquid-liquid equilibrium) binary systems. A group contribution method combined with a statistical associating fluid theory equation of state (GC-PPC-SAFT) proposed earlier by our group (Tamouza, S.; Passarello, J.-P.; Tobaly, P.; de Hemptinne, J.-C. Group contribution method with SAFT EOS applied to vapor liquid equilibria of various hydrocarbons series. Fluid Phase Equilib. 2004, 222-223, 67-76) and recently extended to predict VLE of heavy esters and their mixtures (Nguyen Huynh, D.; Falaix, A.; Passarello, J.-P.; Tobaly, P.; de Hemptinne, J.-C. Predicting VLE of heavy esters and their mixtures using GC-SAFT. Fluid Phase Equilib. 2008, 264, 184-200) is here applied to model vapor liquid liquid equilibria of methanol + glycerol + methyl oleate. The SAFT parameters for the glycerol pure component have been regressed using two association schemes (4C and 3X2B). The dispersive binary interaction parameters k(ij) have been regressed on the binary systems. The group contribution scheme was used for predicting the ester properties.