Nine compounds were detected in three different millipede species: Polydesmus complanatus (L.), Brachydesmus (Stylobrachydesmus) avalae Ćurčić & Makarov, and Brachydesmus (Stylobrachydesmus) dadayi Verhoeff. Benzaldehyde, benzyl alcohol, benzoylnitrile, benzyl methyl ketone, benzoic acid, benzyl ethyl ketone, mandelonitrile, and mandelonitrile benzoate were identified by GC-FID and GC-MS analyses. Hydrogen cyanide was detected qualitatively by the picric acid test. Benzyl ethyl ketone, benzyl methyl ketone, and benzyl alcohol were detected for the first time in polydesmidan millipedes. Benzoylnitrile was the major component in all three hexane extracts. These compounds are suspected to be active in the defensive secretions of these millipede species.