Numerous studies have investigated the presence and the effectiveness of volatile pheromones in Lepidoptera. Conversely, very few studies have focused on the composition and the perception of the relatively low volatile components of cuticular mixtures. Yet, cuticular lipids are implied in the recognition processes of several solitary and social insects. In the present study, the cuticular signatures of the satyrid butterflies Lasiommata megera and Lasiommata paramegaera were examined by gas chromatography. General linear model and discriminant analyses on chemical data clearly revealed large differences between sexes, which showed the same diversification pattern in both species. Moreover, a strong diversification between the two species was found, as were differences among populations. These results represent a first step in demonstrating the communicative function of cuticular compounds in the L. megera/paramegaera complex. Moreover, the discrimination among different species and populations on the basis of cuticular mixtures could represent a platform for studying chemotaxonomy and chemical biogeography in butterflies, as already found in several other insect groups. © 2007 The Linnean Society of London, Biological Journal of the Linnean Society, 2007, 91, 703–710.