AbstractX‐ray diffraction analyses have been performed on samples of electrolytic copper (min. 99,9% Cu) exposed to humid atmoshperes at SO2‐supplies of 10 and 100μg SO2 per cm2 surface area per hour (10 and 100 ppm SO2. respectively). During the SO2 ‐exposures copper (II) sulphate (CuSO4 · 5 H2O) were the only crystalline phases formed in detectable amounts. Interruption of the SO2‐ supply resulted in the formation of copper (I) oxide and antlerite (CuSO4) · 2Cu (OH)2. During prolonged exposure brochanite (CuSO4 · 3Cu(OH)2) and langite (CuSO4· 3Cu(OH)2) and langite (CuSO4 · Cu(OH)2 · 2H2O) were also formed i. E. the Cu:S ratio of the basic copper sulphates increased with time. The formation of antlerite was preceeded by formation of an unidentified intermediate compound, probably a basic copper sulphate with a Cu:S ratio of less than three, and a simultaneous transformation of the copper (II) sulphate and copper (I, II) sulphite formed during the SO2‐exposure.