A multi-component synergistic self-lubricating NiCoCrAl matrix composite was fabricated by high-energy ball milling and spark plasma sintering. The composite exhibited excellent work hardening capability and mechanical properties which mainly attributed to the optimized microstructure and high content of hard reinforced phases. The outstanding self-lubricating property was deriving from the multiple-components synergistic lubricant including Ag, MoS2, LaF3 and CeF3 at room temperature. A continuous smooth tribofilm consisting of various silver molybdates and metallic oxide prevented the direct contact between the Si3N4 ball and the composite resulting in significantly decrease the friction coefficient and wear rate at 800 °C. However, the solid lubrication generated oxidation deterioration without the lubricating effect causing the relative serious worn damage at 400 °C.