In the present work the Gibbs free energy minimization, using a non-linear programming formulation and an approximation in the gas fugacities, was used to calculate the equilibrium composition for supercritical water gasification of methanol, ethanol, glycerol, glucose and cellulose. The proposed formulation mathematically ensures finding the global optimal solution with no need of an initial estimate and the numerical results are close to the ones calculated using non-ideal gas formulation. Therefore, the proposed approach is reliable and easy to use, without numerical difficulties, such as an undesirable local minimum. The model predictions show a good agreement with the experimental studies in all cases studied in this work. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.