A new protocol for the production of deuterium gas from easily-obtainable deuterated methanol and deuterium oxide has been developed. The reaction of deuterated methanol and deuterium oxide in the presence of an iridium catalyst bearing a functional bipyridonate ligand and sodium hydroxide under reflux for 48 hours gave deuterium gas in 63% yield. Deuteration reactions of unsaturated compounds and bromosubstituted aromatic compounds using the generated deuterium gas in the presence of palladium/charcoal catalyst were also investigated.