Biomass steam gasification could be an attractive option for sustainable hydrogen production. Biomass, regarded as carbon neutral emitter, could be claimed as carbon negative emitter if carbon dioxide produced is captured and not allowed to emit to the environment during the process. Thus here an experimental study is carried out to find out the potential of hydrogen production from steam gasification of biomass in presence of sorbent CaO and effect of different operating parameters (steam to biomass ratio, temperature, and CaO/biomass ratio). Product gas with hydrogen concentration up to 54.43% is obtained at steam/biomass = 0.83, CaO/biomass = 2 and T = 670 degrees C. A drop of 93.33% in carbon dioxide concentration was found at CaO/biomass = 2 as compared to the gasification without CaO. Mathematical model based on Gibbs free energy minimization has been developed and is compared with the experimental results. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.