A friendly solid-liquid lubrication system, which is the key to solve the environmental harm caused by phosphorus and sulfur additives in lubricants, has attracted the attention. In this paper, the TiN-Cu/PAO solid-liquid composite system was constructed in situ by tribochemical reaction based on the performance of nitride film and base oil. The results show that when rubbing in PAO, the carbon-based films deriving from PAO will form at the contacting interface. From the perspectives of surface energy, friction products and simulation calculation, the mechanisms of friction and wear reduction of the solid-liquid composite system was systematically investigated. Meanwhile, the degradation process of PAO molecules during friction was revealed from the molecular level, including adsorption, dehydrogenation, C-C bond breaking and reconstruction.