Natural serpentine powders are applicable as additives for various lubricating oils. However, no uniform theories explain their tribological performance, lubrication, and wear mechanism, especially their self-repairing mechanism. Herein, the influence of different nano serpentine powders (NSPs) contents in liquid paraffin on the friction and wear characteristics of steel balls and the self-repairing process of NSPs on the worn surface were studied. Results show that the optimal amount of NSPs was 0.5 wt %. Relative to those of the base oil, the friction coefficients and wear spot diameters were reduced by 22.8% and 34.2%, respectively. Moreover, the long-term tribological test shows that the wear scar diameter decreased slightly after 3 h, reaching the state of dynamic balance between wear and repair. The outstanding tribological performance should be attributed to the formed bilayer tribofilm, the first layer of which contains nanoparticles surrounded by lubricants and the second layer of which contains nanoparticles compacted onto the surface of the steel ball.