The first Italian occurrence of cumengéite, a rare Pb and Cu hydroxychloride, is described from Vesuvius (Italy). Italian cumengéite has a volcanic origin (it occurs in the fumarole), which is unique for that mineral. The mineralogy of Vesuvius’ fumarole is outlined briefly. A powder X-ray diffraction (XRD) pattern of cumengéite is presented. The crystal structure of cumengéite has been refined (R = 0.036) using single-crystal XRD data. Cumengéite is tetragonal, space group I4/mmm, a 15.1007(2), c 24.4940(4) Å. In the structure of cumengéite there are five independent Pb atoms, which are linked to 6–9 anions in five different ways. The structural study revealed the presence of two independent and previously unobserved water molecules, and led to the revision of the accepted chemical formula for the mineral: the new formula is Cu20Pb21Cl42(OH)40·6H2O. Analytical data taken from the literature for cumengéite from Boléo, Mexico (the type locality), as well as a new structural study carried out on the type material confirmed the new formula.