In order to investigate the formation of the multiferroic BiFeO3, the thermal decomposition of the inorganic complex Bismuth hexacyanoferrate (III) tetrahydrate, Bi[Fe(CN)6]·4H2O has been studied. The starting material and the decomposition products were characterized by IR spectroscopy, thermal analysis, laboratory powder X-ray diffraction, and microscopic electron scanning. The crystal structures of these compounds were refined by Rietveld analysis. BiFeO3 were synthesized by the decomposition thermal method at temperature as low as 600 °C. There is a clear dependence of the type and amount of impurities that are present in the samples with the time and temperature of preparation.