The thermodynamic analysis of autothermal reforming of homologue series consisted of ethanol, ethylene glycol, propylene glycol and glycerol representing oxygenated hydrocarbons were studied. The main investigation was to compare the effect of thermoneutral condition where no external air/oxygen supplied for the reaction to sustain and controlled amount of air/oxygen supplied. It was found that the higher number of oxygen atoms in these homologues molecule, the higher tendency of the reaction to be sustained at the desired temperature, and thus it only requires lesser amount of air for heating. The hydrogen selectivity however depends on the ratio of hydrogen atoms with respect to the oxygen atoms in each molecule. The presence of air however, though providing extra heating to the reactor, is offset by a lower hydrogen production. © 2014 Trans Tech Publications, Switzerland.