Pure MoSx as well as MoSx/Pb and MoSx/Ti nanometer-scale multilayers with individual layer thickness in the 4-100 nm range, were prepared by magnetron sputtering at room temperature. The effects of changing the number of interfaces and the effects of changing the percentage of metal (i.e. metal layer thickness) on film microstructure and chemistry have been investigated using SMMS (sputtered neutral mass spectroscopy) depth profiling and X-ray techniques. SNMS depth profiling and X-ray reflection indicate that MoSx/Ti multilayers have a well-defined multilayer structure with sharp interfaces. MoSx/Pb multilayers on the other hand have a poorly defined multilayer structure with broad, diffuse interfaces. There is also evidence that Ti, and to a lesser extent Pb, getter residual oxygen in the vacuum chamber leading to lower oxygen levels within the MoSx layers. X-ray diffraction indicates that the degree of basal (002) orientation is strongly influenced by the number of interfaces in the him as well as by the choice of the metal. The (110) oriented planes are strongly influenced by the MoSx layer thickness, but are relatively insensitive to the metal layer thickness and metal type. X-ray rocking curves indicate that the degree to which the edge-oriented planes have mosaic structure is dependent on MoSx layer thickness, and that this may well be linked to improved tribological performance.