A series of room temperature ionic liquids bearing with phosphonyl groups on the imidazolium cations, namely, 1-(-diethylphosphonyl--propyl)-3-alkylimidazolium tetrafluoroborate, were prepared and their physical properties were determined. They were also evaluated as promising lubricants for the contacts of aluminum on steel by using a SRV test rig. The tribological test results show that the synthetic ionic liquids exhibit better friction-reducing and antiwear abilities than the unsubstituted ionic liquid of 1-ethyl-3-hexylimidazolium tetrafluoroborate (coded as L206) and phosphazene (X-1P). Both the anions and the side substitutes attached to the imidazolium cations affect the tribological performance of lubricants. The scanning electron microscopy, energy-dispersive x-ray analysis, and x-ray photoelectron spectroscopy analyses of the worn surfaces show that complicated tribochemical reactions are involved in the sliding process. The anion decomposition and chemical adsorption of cation took place on the worn surface of aluminum alloy during the sliding process. As a result of the generation of boundary lubrication films which are composed of metal fluorides, , BN, nitrogen oxide, and help to effectively reduce the friction and wear of the contacts.