Crystalline films produced by atomic layer deposition, high binding forces between the film and the substrate induced by chemical adsorption or chemical bonding on the substrate surface will affect the tribological properties of composite coatings. For optimized tribological properties of ZnO-MoS2/ZnO composite coatings, ZnO thin layers of various thicknesses were first manufactured by atomic layer deposition. ZnO-MoS2 coatings were then deposited via radio frequency magnetron sputtering to obtain ZnO-MoS2/ZnO composite solid lubrication coatings. The effects of pre-deposition ZnO thin films on the structure of the subsequent ZnO-MoS2 coatings and the tribological properties of the composite coatings were analyzed. The X-ray diffraction analysis indicates that the pre-deposited ZnO film may induce the deposition and growth of the subsequent ZnO-MoS2 coating. The composite coating with a ZnO film thickness of 100 nm has a wide MoS2 (002) peak. In the meantime, the cross-sectional morphology of the composite coating shows a more compact structure. The obtained composite coating has the lowest coefficient of friction (0.08) and the highest nano-hardness (2.33 GPa). H/E shows that the wear resistance of the composite coating is also improved. The results of X-ray photoelectron spectroscopy show that approximately 5 at.% free S on the surface of the composite coating under atmospheric conditions, indicating improved moisture resistance. Atomic layer deposition and radio frequency magnetron sputtering methods reveal that pre-deposited ZnO thin film has a strong effect on the structures of subsequent ZnO-MoS2 coatings, providing insights into the effect of ZnO in MoS2-based solid lubrication coatings. According to the analysis of the growth of ZnO thin film and its influence on the growth of subsequent ZnO-MoS2 coating, a worn model for ZnO-MoS2/ZnO composite coating was put forward. The schematic diagram assumed that factors of ZnO thin film-substrate bonding force, brittleness of ZnO thin film, and chemical adsorption between ZnO-MoS2 coating and ZnO thin film layers resulted in lubrication properties of the composite coatings. A brittle fracture in the ZnO thin film was likely to occur as the thickness increased. Therefore, an overly thick ZnO film must be avoided. The chemical binding force of the ZnO thin film-substrate was generally greater than the adherence of the subsequent ZnO-MoS2 coating to the ZnO thin film layers, therefore reducing the mismatch between the ZnO-MoS2 coating and the ZnO thin film would be benefit to the lubrication of composite coatings. The influence of ZnO thin film on the structure and tribological properties of the composite coating has been clarified. In short, both the nanocrystalline coating and adhesive force between the ZnO thin film and the substrate reduced the coefficient of friction and improved the wear-resistance of the ZM100 coating. The trend of friction coefficient from high to low and the ultimate wear failure of ZnO-MoS2 coatings deposited on ZnO thin films with a thickness of 200 nm were also explained. Overall, the tribological properties of ZnO-MoS2/ZnO composite coatings can be improved effectively by the optimized atomic layer deposition process. The optimal interface combination between ZnO thin film, substrate and ZnO-MoS2 can be achieved by controlling the thickness of ZnO thin film, so as to fabricate ZnO-MoS2/ZnO composite coatings with better tribological properties and long service life.