In the present study, the chemical composition of the essential oil from aerial parts of a very rare Centaurea species, not previously investigated, Centaurea erycina Raimondo and Bancheva, collected in Sicily, was evaluated by GC-MS. The new species, classified just twenty years ago, belongs to Centaurea cineraria group (sect. Pannophyllum Hayek, Asteraceae) and grows in an extremely limited area in the NW part of Sicily. The oil was shown to be rich of aldehydes (41.4%) and sesquiterpenes (33.4%). The main components of the essential oil were β-caryophyllene (13.4%), caryophyllene oxide (12.6%), hexanal (11.9%), and trans-2-hexenal (10.0%). Furthermore, a complete literature review on the composition of the essential oils of all the other taxa of Centaurea, belonging to sections Pannophyllum, studied so far, was carried out.