A series of novel metal halide-stabilized linear phosphazene derivatives were synthesized. The friction-reducing and antiwear abilities of the resulting products as the lubricants for a steel-on-steel contact were comparatively investigated on an Optimol SRV oscillating friction and wear tester. The morphology of the worn steel surface was observed on a scanning electron microscope, while the chemical states of some typical elements on the worn steel surface were examined by means of X-ray photoelectron spectroscopy. It was found that both the side branch structures and central metals influenced the friction-reducing and antiwear behaviors of the synthetic derivatives as the lubricants, which was related to the different adsorption activities of the organic compounds composed of different organic ingredients and metallic ions on a nascent metal surface. All the synthetic lubricants except for the iron (III) derivative showed increased antiwear abilities with increasing metallic ionic radius. A protective layer originated from the tribochemical reaction together with the adsorbed boundary lubricating layer containing organic fluorine compounds, nitrogen oxide, and Fe 3 (PO 4 ) 2 plays an important role in improving the friction and wear behavior of the steel-on-steel system. A series of novel metal halide-stabilized linear phosphazene derivatives were synthesized. The friction-reducing and antiwear abilities of the resulting products as the lubricants for a steel-on-steel contact were comparatively investigated on an Optimol SRV oscillating friction and wear tester. morphology of the worn steel surface was observed on a scanning electron microscope, while the chemical states of some typical elements on the worn steel surface were examined by means of X-ray photoelectron spectroscopy. It was found that both both side branch structures and central metals influenced the friction-reducing and antiwear behaviors of the synthetic derivatives as the lubricants, which was related to the different adsorption activities of the organic compounds composed of different organic ingredients and metallic ions on a nascent metal surface. (III) derivative showed increased antiwear abilities with increasing metallic ionic r adius. A protective layer originated from the tribochemical reaction together with the adsorbed boundary lubricating layer containing organic fluorine compounds, nitrogen oxide, and Fe 3 (PO 4) 2 plays an important role in improving the friction and wear behavior of the steel-on- steel system.