Perfluoroalkyl iodides react directly with trialkylbismuth compounds at 100°C to form dialkylperfluoroalkyl- and alkylbisperfluoroalkylbismuthines. These previously unknown compounds decompose below their boiling points. They are readily oxidized and may be hydrolysed by aqueous alkali, liberating the appropriate fluorocarbon. Halogens rapidly split off both alkyl and perfluoroalkyl groups. Whereas interconversion of the mixed alkylperfluoroalkyl compounds readily occurs, attempts to form the fully perfluoroalkylated bismuth compounds have been unsuccessful. Vapour pressure-temperature and infrared spectral data are presented and discussed.