The process of high-temperature oxidation of EuS in the air was explored in the temperature range of 500–1000 °C. The oxidation reaction enthalpy was determined (ΔH0exp = −1718.5 kJ/mol). The study of oxidation products allowed to establish the mechanism of EuS oxidation with oxygen. At 500–600 °C, EuS is oxidized to a mixture of Eu3+-containing compounds (Eu3S4, Eu2O2S). In the range of 700–1000 °C, only europium oxysulfate Eu2O2SO4 is formed. The structure refinement for Eu2O2SO4 was performed by the Rietveld method. The luminescence intensity of europium oxysulfate Eu2O2SO4 with characteristic 4f-4f transitions from the 5D0 state was investigated as a function of oxidation temperature.