The nano-multilayered structure results in an increased harness but a decreased adhesion of the films. An increasing layer thickness ratio of a-C to WSx raises the sulphur content of the WSx sublayer. The effects of layer thickness ratio of a-C to WSx on microstructure of the films are negligible. The multilayer films exhibit the best wear resistance in vacuum compared with in humid air and in distilled water. The tribological properties of the multilayer films are much better than single WSx film in various test environments.