The origin of agricultural products is gaining in appreciation while often hard to determine for various reasons. Geographical origin may be resolved using a combination of chemical and physical analytical technologies. In the present case of Lily of the Valley ( Convallaria majalis) rhizomes, we investigated an exploratory set of material from The Netherlands, three other European (EU) countries and China. We show that the geographical origin is correlated to patterns of stable isotope ratios (isotope fingerprints) and volatile organic carbon (VOC) compounds (chemical fingerprints). These fingerprints allowed clear distinction using exploratory and supervised statistics. Isotope ratio mass spectrometry of 12C/ 13C, 14N/ 15N and 16O/ 18O isotopes separated materials from Europe and China successfully. The VOC patterns measured by Proton Transfer Reaction Mass Spectrometry (PTR-MS) allowed distinction of three groups: material from The Netherlands, the other EU countries and China. This knowledge is expected to help developing a systematic and efficient analytical tool for authenticating the origin of flower bulbs.