Effects of trace oxygen on iron sulphides‐supported catalysts (FeSx/γ‐Al2O3) were evaluated through smelter off‐gas reduction process for sulphur synthesis. Catalytic performance was evaluated under different oxygen content conditions. The properties of fresh and used catalysts were investigated by means of X‐ray diffraction (XRD), thermogravimetry‐differential thermal analysis (TG‐DTA), X‐ray photoelectron spectroscopy (XPS), and elemental analysis and relationships of active phases and activity were analyzed. The relationship between different active crystal crystals (FeSx, FeS2, Fe, FeO, γ‐Fe2O3) and SO2/O2 adsorption and conversion was investigated. The mechanism of oxygen influence on the FeSx/γ‐Al2O3 surface was given and the lifetime of the catalyst in the reaction atmosphere close to real smelter off‐gas after dust and oxygen removal steps containing trace oxygen (0.5 O2 v/v.%) was explored.