The formation conditions of anti-wear tribofilms by layered silicates, as well as the structure and evolution of the tribofilms are not clear. Herein, the anti-wear properties of organically modified halloysite nanotubes (HNTs) were investigated under varied forms of wear. The findings indicated that the HNTs exerted the best anti-wear effect (34.55%) when the friction surface was dominated by abrasive wear. This is attributed to the formation of anti-wear tribofilm on the surface of the substrate. And the evolution of the anti-wear tribofilm was further investigated. The results revealed that the main components of the anti-wear tribofilm were aluminum oxides, silicon oxides, iron oxides, and amorphous carbon. And the anti-wear tribofilm underwent an amorphous - nanocrystal - amorphous evolution with the increase of wear time. The formation mechanism of the tribofilm can be summarized as physical spreading - phase change decomposition - polishing oxidation - cleavage deposition.