The pentaerythritol (PE)-pentaglycerine (PG)-neopentylglycol (NPG) ternary system has been thermodynamically assessed using the CALPHAD method and Thermo-Calc software. The PE-PG, PG-NPG, PE-NPG binary systems have also been calculated using CALPHAD on the basis of reported binary experimental data. The solution phases are modeled as substitutional solutions, in which the excess Gibbs energies are expressed by the Redlich-Kister-Muggianu polynomial. The PE-NPG binary phase diagram was modeled using Henrian solution model, and the liquid phase was assumed ideal. The PG-NPG system was optimized using regular and sub-regular solution models and show invariant equilibria at 298 K. The PE-NPG binary system was calculated from room temperature to the liquid phase temperatures. The modeled phase diagrams and the experimental data are in good agreement. A set of self consistent thermodynamic parameters formulating the Gibbs energies of various phases in the PE-PG-NPG ternary system are obtained in the present work. Thermodynamic properties, several vertical and isopleth sections have been calculated and are in good agreement with experimental data. (C) 2012 Published by Elsevier B.V.