Volatile metabolites from Frullania brasiliensis Raddi, Herbertus juniperoideus (Sw.) Grolle, Leptoscyphus hexagonus (Nees) Grolle, and Syzygiella anomala (Lindenb. & Gottsche) Steph collected in the south of Ecuador were investigated. Volatile secondary metabolites were extracted by hydrodistillation and analyzed by gas chromatography/flame ionization detector (GC/FID) and Gas chromatography/Mass spectrometry (GC/MS). Sixty-seven volatile compounds were identified in the four species, which represent between 80.12–90.17% of the total chemical composition. The major components were τ-muurolol (32.14%) and Germacrene-D (11.98%) in the essential oil of F. brasiliensis, bicyclogermacrene (18.23%), and Caryophyllene oxide (15.29%) in the oil of H. juniperoideus, Cabreuva oxide D (33.77%) and Elemol (18.55%) in the oil of Leptoscyphus hexagonus, and Silphiperfola-5,7(14)-diene (25.22%) and Caryophyllene oxide (8.98%) in the oil of Syzygiella anomala. This is the first report on volatile compounds for the species Herbertus juniperoideus, Leptoscyphus hexagonus, and Syzygiella anomala.