Because of their excellent tribological properties and potential to replace problematic lubricant additives currently in use, WS 2 nanoparticles have spurred considerable interest over the last two decades from academia and industry to decipher their mechanism of action. To elucidate the mechanism, this study carried out tribological tests at low and high temperatures and investigated the wear track and friction properties. It was found that in highpressure, high-temperature sliding contacts, WS 2 nanoadditives react with the metal substrate to generate thick chemical tribofilms which account for their excellent tribological properties. Based on XPS and FIB/SIMS results, a layered structure was proposed for the chemically formed tribofilms. The large amount of W in the composition of the reacted tribofilm could explain the excellent mechanical and antiwear properties, while the exfoliated squashed WS 2 NPs which fill the gaps and cover the reacted tribofilm account for the striking reduction in the boundary friction.