The reaction between a biomass (cellulose, sucrose, glucose, starch, cotton, or Japanese paper) and NaOH in the presence of water vapor produced pure hydrogen without CO and CO2 at temperatures in the range 473-623K. The addition of Ni/Al2O3 or Rh/Al2O3 catalyst to cellulose enhanced the production of hydrogen at < 573 K. The reaction between cellulose and NaOH can be written as: C6H10O5 + 12NaOH + H2O = 6Na(2)CO(3) + 12H(2). The reactivities of alkali metal hydroxides were: KOH > NaOH >> MOH. (C) 2004 Society of Chemical Industry.