The phytochemical investigation of Dimerostemma arnottii (Asteraceae) afforded, in addition to a known eudesmanolide, two unusual eudesmane methyl ester derivatives and a new eudesmanolide. Structural elucidation of the compounds was based on their 1D and 2D NMR spectroscopic as well as HR-ESI-MS data. There is a remarkable similarity between the structures of the eudesmanes from D. arnottii and those previously encountered in other Dimerostemma species, which is in agreement with the results of a previous phylogenetic study based on molecular data. The chemotaxonomic relevance of the isolated compounds is briefly discussed.