Production of hydrogen rich gas from gasification of biomass was studied at bench-scale using oxygen as the gasifying agent. A series of experiments were performed to investigate the effects of different operating parameters on the performance of the gasification process. These included the oxygen to fuel equivalence ratio (0.12–0.4), reaction temperature (700–850 °C), reaction residence time (45–120 min), and catalyst type. The catalysts selected are marly clay, calcium hydroxide, dolomite, and cement kiln dust. Within the range of the experimental conditions tested, the results suggest that the best operating conditions for the gasification process are; temperature, 800 °C, an oxygen to fuel ratio of 0.25, a reaction time of 90 min, and calcined cement kiln dust as a catalyst. The results have also demonstrated that the product gas from gasification of cotton stalks with calcium hydroxide has higher H2 and CO concentration (45 and 33%). In addition gasification of cotton stalks with calcined cement kiln dust resulted in higher hydrogen and CO enrichment as well as higher overall gas yield (39vol%, 33vol%, and 1.5 m3/kg) compared to other agriculture residues of corn stalks and rice straw.