Arneis is an Italian autochthonous white grape cultivar. This study involved investigating the chemicophysical, aromatic composition and sensory evaluation of Arneis wine in relation to different oenological practices during winemaking and ageing. For the first time, polyfunctional thiols related aromas were identified above their perception threshold in Arneis wine. Moreover, citrus, grapefruit and tropical fruit notes characterized this wine during the first month of ageing, thus suggesting a strong correlation between chemical and sensory results. The concentration of thiols decreased rapidly during the first month of ageing, together with the tropical fruit notes. In particular, the perception of the grapefruit note of the wine decreased in association with the 3-mercaptohexyl acetate content in both the barrel and stainless steel (ST) aged wines. Moreover, the ageing technique clearly affected wine composition and sensory profile; barrel aged wines were characterized both by vanilla and honey notes, and a weaker perception of thiols despite containing a similar concentration to ST aged wines. Within this study, the ability of glutathione to decrease the oxidation of volatile thiols in Arneis wine was confirmed, but under experimental conditions employed, the addition of reduced glutathione did not lead to any statistically significant differences in sensory results.