This work presents the autothermal reforming (ATR), or called oxidative steam reforming (OSR), of ethanol for hydrogen production. A thermodynamic analysis of product distribution for ATR from ethanol has been performed by using the method of Gibbs free energy minimization. The effect of steam-to-carbon (S:C) and air-to-carbon (A:C) molar ratios under adiabatic temperature of ATR reactor on chemical equilibrium composition of hydrogen rich stream is investigated. An increase of S:C ratio increases an efficiency of hydrogen production while carbon monoxide formation decreases but, however, more energy consumption for preheating reactants is also needed. An increase of A:C ratio in the range between 0 and 1.75 causes an increase of hydrogen yield but at greater A:C ratio, a decrease of hydrogen production and more water formation can be found. The results of the thermodynamic equilibrium show that the predicted hydrogen composition in the reaction of fuel-water-air system at constant temperature is higher than that obtained from experiment in both the absence and presence of catalysts in the OSR reaction when the temperature is fixed at 700 °C. The predicted carbon monoxide is lower than that obtained from the results of non-catalytic reaction but higher than that attained from the presence of catalyst in process.