Uzon caldera, located in the eastern volcanic belt of the Kamchatka peninsula, is a complicated structure of Middle Pleistocene age. The composition of the co-existing solid and fluid phases, temperature and pH were determined with the aim of establishing the distribution of sulphur species, As, Sb and the main ore-forming metals. In the solid samples, the following sulphur-bearing minerals were identified: pyrite, realgar, orpiment, alacranite (As 8S 9), uzonite (As 4S 5), amorphous As-sulphide, stibnite, cinnabar and native sulphur. The following sulphur-bearing species H 2S, H 2S 2+S 5 2−(aq)(aqueous polysulphanes), S 0(aq), SO 3 2−(aq), S 2O 3 2−, SO 4 2− and total concentration of sulphur were determined in solutions. Eh, pH and H 2S concentration were measured potentiometrically in situ. Zero-valent sulphur (S 0(aq)+H 2S 2+S 5 2−(aq)) predominates in Uzon solutions. The pair H 2S–S colloidal is Eh-determining in Uzon solutions up to 75–85°C. A quantitative thermodynamic model of the mineral deposition process at Uzon was constructed using the collected data. It was obtained that the composition of the hydrothermal solution and the precipitation of Sb–As–Hg species can be described using two only main factors: the initial composition of fluid and the temperature variation.