Leguernite, ideally Bi12.67O14(SO4)5, is a new mineral found in high-temperature fumarolic assemblages at La Fossa crater, Vulcano, Aeolian Islands, Italy. It occurs as aggregates of needle-shaped crystals associated strictly with anglesite, balićžunićite and an unknown Bi sulfate. Leguernite is colourless to white, transparent, non-fluorescent, has a sub-adamantine lustre and a white streak. Electron microprobe data led to the chemical formula (on the basis of 34 anions p.f.u.) (Bi12.40Pb0.15)Σ=12.55S5.08O34. The calculated density is 7.375 g cm−3. A Raman spectrum collected on a single crystal of leguernite confirmed the anhydrous nature of the mineral.
Leguernite is monoclinic, space group P2, with a = 11.2486(11), b = 5.6568(6), c = 11.9139(10) Å, β = 99.177(7)°, V = 748.39(12) Å3 and Z = 1. The crystal structure is built up of Bi–O blocks of a fluorite-like structure with Bi12O14 composition separated by a single sulfate ion along  and by groups along . It can also be described as composed of (001) layers with composition [Bi12O14(SO4)6+]n alternating with layers of composition along . Leguernite shows significant similarities with the synthetic Bi14O16(SO4)5 compound.
The eight strongest reflections in the powder X-ray diffraction data [d in Å (I) (hkl)] are: 3.220 (100) (013), 3.100 (95) (3İ11), 2.83 (30) (020), 2.931 (25) (302), 2.502 (25) (3İ04), 2.035 (20) (322), 1.875 (20) (3İ24) and 5.040 (15) (110).
The name is in honour of François “Fanfan” Le Guern (1942–2011), who was a very active volcanologist and specialist in volcanic gases and sublimates. Both the mineral and the mineral name have been approved by the IMA-CNMNC (2013–051).