Six different olibanum samples with certified botanical origin were analyzed by headspace SPME-GC/MS in order to define their mono-, sesqui- and diterpenic composition, as pertinent criteria of identification. Boswellia carteri and Boswellia sacra olibanum have quite similar chemical composition, with isoincensole acetate as the main diterpenic biomarker. Although Boswellia serrata olibanum also exhibits this biomarker, the presence of methylchavicol, methyleugenol and an unidentified oxygenated sesquiterpene distinguishes B. serrata olibanum from the two other species. The characteristic chemical compounds of Boswellia papyrifera are the diterpenic biomarkers incensole and its oxide and acetate derivatives, n-octanol and n-octyl acetate. Boswellia frereana olibanum is devoid of diterpenes of the incensole family but contains a high amount of many dimers of alpha-phellandrene. The chemical composition of olibanum, which is demonstrated to be different for each Boswellia species allowed the determination of the taxonomic origin of frankincense samples purchased on various markets in East Africa, in the Near East and in Yemen. Moreover, terpenic fingerprints allowed the botanical origin of olibanum used in traditional incense mixtures to be identified. Furthermore, this study gave us the opportunity to assign a botanical origin to an archaeological frankincense sample.