The chemical compositions of hexane extracts of the lipid fraction of the roots of the medicinal Boraginaceous species Alkanna tinctoria, Onosma heterophylla, Macrotomia densiflora and Onosma hispidium are presented and their phytochemical relevance evaluated. The predominating fatty acids in all of the root lipids were stearic, palmitic, oleic, linoleic and gamma-linolenic acids, while the latter and stearidonic acid predominated in the seeds and leaves of various Boraginaceous species. The indigenous presence of methyl, ethyl and isopropyl esters of fatty acids, reported for the first time in the roots of higher plants, is considered to be of particular importance in the biosynthesis of fatty substances. The results suggest the use of fatty acids as chemotaxonomic markers for Boraginaceous species and the utilisation of Boraginaceous species as new commercial sources for fatty acids with valuable medicinal and nutritional properties.