Arnica montana is a plant distributed in most of Europe, including the Alpine arc and Apennines in Italy, and traditionally used worldwide for medicinal properties. Twelve natural populations of the species from Trentino-Alto Adige, Italy, were characterized using Headspace-Solid Phase Microextraction analysis for their volatile profile. Fifty-one compounds were detected in flower heads, the most abundant being (E)-Caryophyllene (23.4 %), 2,2,4,6,6-Pentamethylheptane (8.3 %), αtrans-Bergamotene (7.2 %), Germacrene D (5.7 %), and Hexanal (5.3 %). A multivariate analysis performed on the ten most abundant compounds grouped these investigated accessions into five main clusters. Three clusters, comprising together five accessions, were linked to the geographical origin of two collection sites. This work is a complete characterization of volatiles of the species by SPME analysis reported to date. Furthermore, results suggest that the species' volatile profile can be linked to the geographical origin of the natural populations and, therefore, represent a tool for evaluating biodiversity within the species.