Thermodynamics of glycerol partial oxidation for hydrogen production has been studied by Gibbs free energy minimization method. The optimum conditions for hydrogen production are identified: reaction temperatures between 1000 and 1100 K and oxygen-to-glycerol molar ratios of 0.4-0.6 at 1 atm. Under the optimal conditions, complete conversion of glycerol, 78.93%-87.31% yield of hydrogen and 75.12%-87.97% yield of carbon monoxide could be achieved in the absence of carbon formation. The glycerol partial oxidation with O-2 is suitable for providing hydrogen-rich fuels for Molten Carbonate Fuel Cell and Solid Oxide Fuel Cell. The carbon-formed and carbon-free regions are found, which are useful in guiding the search for suitable catalysts for the reaction. Inert gases have a positive effect on the hydrogen and carbon monoxide yields. (c) 2010 Elsevier B.V. All rights reserved.