A new nanostructured Bi(III) supramolecular compound, {[Bi(2)(4,4'-Hbipy)(1.678)(4,4'-Hbipy)(0.322)(micro-I)(2)I(5.678)] (4,4'-bipy)} (1), 4,4'-bipy=4,4'-bipyridine} was synthesized by a sonochemical method. The nano-structure of 1 was investigated using scanning electron microscopy, powder X-ray powder diffraction (XRD), IR spectroscopy and elemental analysis, and the crystal structure of compound 1 was determined by single-crystal X-ray diffraction. The thermal stability of bulk compound 1 and of nano sized particles was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Bi(2)O(3) and BiI(3) nano-structures were obtained by calcinations of nano-structures of compound 1 at 400 degrees C under air and nitrogen atmospheres, respectively.