A chemical equilibrium model was developed to predict the product composition of a biomass gasification system using highly preheated air and steam. The advantages and limitations of this system were discussed from a thermodynamic viewpoint. The first and second law analyses have been conducted for various preheating temperatures and steam/biomass mass (S/B) ratios. The results demonstrated that the chemical energy output of the produced syngas is highest when the S/B ratio is 1.83 under the conditions used in this study. However, higher S/B ratios have a negative effect on the energy and exergy efficiencies. Higher preheating temperatures increase the chemical energy of the produced syngas and the two efficiencies. The peak values for the energy and exergy efficiencies are 81.5% and 76.2%, respectively. Based on the calculated limitation values, where the highest chemical energy (exergy) of the produced syngas and maximum achievable efficiencies are determined, a thermodynamically possible operating region is suggested.