The interaction of Bi(III) with aqueous solution of sulfamic acid is investigated, and a new compound with the following composition [Bi6O4(OH)(4)](NH2SO3)(6) is derived. The substance obtained is characterized by various methods: elemental analysis, DTA, TG, FTIR and X-ray diffraction. Based on the experimental results, a mechanism of thermal decomposition of the newly synthesized compound is proposed. (C) 2010 Elsevier B.V. All rights reserved.