Volatile terpenes have been proposed as chemotaxonomic markers, despite the strong environmental control on their synthesis. To clarify whether chemical profiles match biological diversity, cork oak, a monoterpene-emitting species that has been bred by humans and frequently hybridizes with other oaks, is a useful case-study. Analysis of the available genetic information in cork oak provenances suggests that volatile terpenes might indeed suitably track geographical diversity even at the intraspecific level. Phylogeographical diversity does not reflect chemical diversity in other evergreen oaks that have not been intensively bred. Breeding for productive traits might therefore drive selection for terpene diversity, in turn modulating important adaptive mechanisms against biotic and abiotic stressors.