In order to improve the tribological properties of perfluoropolyethers (PFPE), fluorinated candle soot is adopted as the lubricant additive because of their special onion-like structure. The candle soot particles (CSP) are modified by 1H,1H,2H,2H-perfluorooctanol (CSP-PFHE nanoparticles), and after the fluorination, they exhibit good dispersivity in PFPE. The mixtures composed of CSP-PFHE nanoparticles and PFPE possess better tribological performance than neat PFPE under different test conditions including variable temperature, the irradiation of atomic oxygen and extreme pressure. The reason can be attributed to that the graphene layers are exfoliated from the surfaces of nanoparticles and adhere onto the steel surfaces to form the tribofilm, which can protect the sliding pairs surfaces from friction and severe wear. Meanwhile, the redundant nanoparticles act as the rolling bearing between the sliding surfaces to decrease the wear and some are packed into the corrosion pits generated by PFPE to prevent further erosion in the process of friction. At the end, the lubricating mechanism of CSP-PFHE nanoparticles as additives of PFPE is proposed based on the test results of scanning electron microscope, contact electrical resistance and X-ray photoelectron spectroscopy.