The tribological effects of tetraalkylphosphonium phosphate ionic liquids (PP-ILs) as lubricants and lubricant additives of multialkylated cyclopentanes (MACs) was evaluated in vacuum (10 −4 Pa) by a vacuum four-ball tribometer. Results showed that the transient seizure-like high friction appearing for MACs could be effectively eliminated by neat PP-ILs or by adding the PP-ILs with long alkyl chain into MACs. Confirmed by the surface analysis, the improved tribological performances could be ascribed to the high load-carrying capacity of ionic liquids and the protective films formed on the contact surfaces through the tribochemical reaction between the PP-ILs and fresh steel surfaces under the boundary lubrication.