The hexylenediammonium pentachlorobismuthate, NH3(CH2)6NH3BiCl5 crystal has been studied by means of XRD, DSC and spectroscopy (IR and Raman)techniques. The X-ray powder study develooped at different temperatures showed that the crystal exhibits two phase transitions near 286 K and 326 K. The DSC analysis (on heating and couling) confirmed the existence of these phase transitions at 291/286 K and 326/325 K. The Raman spectroscopy study made at various temperatures showed that both anionic and cationic motions contribute to the complex transition mechanisms.