To improve the tribological properties of WS₂ film both in vacuum and in humid air conditions, its microstructure was optimized by doping different concentrations of Cu via radio frequency co-sputtering method. The film microstructure and composition were investigated by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, grazing incidence X-ray diffraction and high-resolution transmission electron microscopy. It was verified that Cu was presented in amorphous phase in the WS₂ matrix and could also induce amorphization and densification of the composite films gradually. The film microstructure changed from coarse columnar platelet structure at low Cu content (0–5.8 at.%) to transition structure with two separate layers at increased Cu content (11.5–16.2 at.%) and to a featureless structure at high Cu content (above 24.4 at.%). The mechanical and tribological properties of films were evaluated using the scratch tester and ball-on-disk tribometer, respectively. It was found that the incorporation of a suitable content of Cu dopant could significantly improve the film toughness, but excess amount of Cu dopant lead to high brittleness. All the composite films exhibited much lower wear rate and longer wear life than those of pure WS₂ film both in vacuum and in humid air conditions. The wear mechanisms were proposed after correlating the mechanical performance with film microstructure.