Multilayer ZnS/CdS thin films were grown on glass, ITO-covered glass and (100)GaAs substrates by successive ionic layer adsorption and reaction (SILAR) technique at room temperature and ambient pressure. The layers in multilayer thin film structures were nominally 1–6 nm thick and the amount of layers varied so that the total thickness of 100–120 nm was achieved. The films were polycrystalline according to X-ray diffraction analysis and scanning electron microscopy. The interfaces between the separate cadmium sulfide (CdS) and zinc sulfide (ZnS) layers were not sharp, but contained thin CdxZn1−xS solid solution layers. Annealing enhanced the mixing of the different layers and after 50 h at 300°C no separate CdS and ZnS X-ray reflections could be detected. About 20 nm thick layers could be detected as separate fields by scanning electron microscopy.