Bisphenol S bis(diphenyl phosphate) (BSDP) was synthesised and characterised, and its tribological behaviours as additives in polyurea grease and lithium complex grease were evaluated for steel/steel contact at 200 °C. The results indicated that BSDP could dramatically reduce the friction and wear of sliding pairs in the base grease of polyurea, and the tribological performances of BSDP in polyurea grease were significantly superior to the normally used molybdenum disulfide-based additive package. Furthermore, BSDP in polyurea grease has better tribological behaviour than that in lithium complex grease at a constant load of 100 N. X-ray photoelectron spectroscopy analysis indicated that boundary lubrication films composed of Fe(OH)O, Fe₂O₃, Fe₃O₄ and FePO₄ compounds containing the P–O bonds and nitride compounds were formed on the worn surface, which resulted in excellent friction reduction and antiwear performance.