The study included 15 lichen species analysed for volatile substances by gas chromatography/mass spectrometry after collection by an adsorption technique. We show that lichens emit characteristic blends of volatile compounds, such as: fatty acid derivatives, isoprenoids and benzenoids. We detected 104 volatiles, the most widespread being toluene and nonanal (found in all 18 accessions), thereafter 1,4-xylene and β-pinene (17 accessions), decanal (16 accessions) and 3-methoxy-1,2-propanediol (15 accessions). 23 volatiles were restricted to just a single accession, thus not informative in grouping the species. We did not find any clear phylogenetic signal with respect to the mycobiont or the phycobiont. In several cases, congeneric species displayed strongly divergent volatiles spectra, indicating divergent selection. We discuss possible biotic explanations for the observed volatiles diversity. Fruiting bodies of lichens, so called apothecia, are often eaten by various small organisms such as mites and collembola and one function of the volatiles could be for protection or attraction. The present study connects to earlier work on plant volatiles, insect pheromones and analytical techniques.