Carbohydrates such as glycerol and D-Glucose can be directly converted to synthesis gas products near equilibrium on RhCe/Al2O3 catalysts at residence times less than 70 milliseconds. With the addition of the steam, ∼80% of the hydrogen in glycerol can be converted directly to H2. Selectivity to H2 and CO from D-glucose was observed ∼50% near equilibrium maintaining 2/3 of the carbohydrate fuel value. Autothermal conversion is likely to occur by coupling the endothermic decomposition process with highly exothermic catalytic partial oxidation. By directly contacting carbohydrate particles with a hot catalytic surface capable of providing high heating rates, the solid particle forms volatile organics which flow into a porous catalyst and reform with oxygen from air to form synthesis gas. Deactivation over 20 hrs of operation was not detected, possibly because the formation of char is limited by high particle heating rates.