This work investigated the lubricating and anti-wear properties of several sulfur additives for a nickel-based superalloy-tungsten carbide friction pair. Compared with PAO40 without any active chemical compounds, the three kinds of sulfur additives could decrease the friction coefficient from 0.2 to 0.1 and the wear volume by 90%. Sulfurized fatty acid ester had the best performance under high temperature and heavy load with COF below 0.1 and the smallest wear volume. Furthermore, the lubricating mechanism was investigated by XPS. The physical adsorptive film and the tribochemical film together enhanced the friction-reducing and anti-wear performances of the lubricants. This effective lubricant for Inconel 718 can be applied to the machining of nickel-based alloy.