Inorganic fullerene-like tungsten disulfide particles have been proved to have good anti-friction and anti-wear properties as lubricating materials. As far as we know, however, when it is used as a lubricant additive, its behavior and action mechanism in the friction process are rarely studied. Herein, IF–WS2 particles were synthesized by a Chemical Vapor Deposition (CVD) method. The effect of IF–WS2 particle concentrations in the PAO6 oil on the tribological behaviors was investigated with a four-ball wear machine at both 75 and 100 °C. Additionally, the analyzed morphology and composition of nanomaterials and worn surfaces were analyzed by Scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The friction behavior in actual working conditions was studied by a wear testing machine. The experimental results show that compared with the original PAO6 oil, at a dispersion of 0.25 wt% in PAO6 oil, the IF–WS2 particles showed the best performance in terms of coefficient of friction, wear scar diameter and wear mass, which significantly reduced by 27%, 43% and 87%, respectively. At the same time, in the process of friction, it was found that IF–WS2 particles accumulated in the depressions to fill the scratches, and adsorption films and chemical films, including FeS2, WS2 and WO3, were formed on the worn surfaces to avoid the direct contact among the friction pairs more effectively, resulting in the improved anti-wear performances. Additionally, the addition of IF–WS2 particles effectively delayed the rise of lubricating oil temperature. In addition, dispersant span 80 can effectively improve the dispersion and stability of IF–WS2 in PAO6. This work provides us for understanding the effective lubrication mechanism of IF–WS2 particles in more detail and having a new acknowledge of the comprehensive performance of IF–WS2/PAO6 oil.