Calcium fluoride (CaF2) nanocrystals with average grain size of 60 nm were synthesized via a precipitation method. The morphology and structure of nanocrystals were characterized by means of transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). TEM and XRD showed that CaF2 nanocrystals are cubic particles in submicron scale. The tribological properties of the prepared CaF2 nanocrystals as an additive in lithium grease were evaluated with a four-ball tester. The results indicated that these nanocrystals exhibit excellent antiwear, friction reduction and extreme pressure (EP) properties, It was also found that the EP and antiwear capabilities of the grease are not proportional to the content of CaF2 nanocrystals but there existed a certain value. The rubbed surface after friction test was investigated with X-ray photoelectron spectroscopy and scanning electron microscopy to understand the action mechanism. The results show that a boundary film mainly composed of CaF2, CaO, iron oxide and some organic compounds was formed on the rubbed surface after friction test and the thickness of boundary film was about 12 nm. The disproportion of stoichiometric ratio of Ca and F in boundary lubrication film indicates that tribochemical reaction of CaF2 nanocrystals occurred on the worn steel surface at severe tribological conditions. (c) 2007 Elsevier Ltd. All rights reserved.