This paper describes the synthesis, structure, and tribological behavior of nanocomposite tungsten disulphide (WS 2) solid lubricant films grown by atomic layer deposition. A new catalytic route, incorporating a diethyl zinc catalyst, was established to promote the adsorption and growth of WS 2. The films were grown down to 8 nm in thickness by sequential exposures of WF 6 and H 2S gases in a viscous flow reactor on Si, SiO 2, stainless steel, and polycrystalline Si and electroplated Ni microelectromechanical systems structures. Films were studied by cross-sectional transmission electron microscopy (XTEM) with Automated eXpert Spectral Image Analysis (AXSIA) software for X-ray spectral images and X-ray diffraction to determine the coating conformality and crystallinity. The coatings exhibited a hexagonal layered structure with predominant preferentially orientated (0 0 2) basal planes. Regardless of orientation to the substrate surface, these basal planes when sheared imparted low friction with a steady-state friction coefficient as low as 0.008 to 50,000 cycles in a dry nitrogen environment. The formation of smooth transfer films during wear provided low interfacial shear stresses during sliding thus achieving low friction and wear. The XTEM combined with AXSIA of the wear tracks identified this mechanism and the effects of vapor phase reaction by-product etching on insulating and native polycrystalline Si and Ni surfaces.