Nano-BN/Si and BN/Al2O3 composite lubricants was prepared by a hydrothermal stirring synthesis method. Orthogonal experiments were conducted by changing the mass fraction of Si and Al2O3. The extreme pressure and wear resistance performance of nano-BN lubricants were investigated using the four-ball machine method. The effect of nano-BN on the friction and wear performance of AlN plates was studied using multifunctional friction and wear tests. SEM, EDS, and XPS were used to characterize the wear morphology and element distribution on the wear surface of the steel balls and the sliding AlN plates. The wear and friction mechanism of nano-BN/Si and BN/Al2O3 as anti-wear additives contained in the nano-composite lubricants between the metal friction pairs were proposed. The excellent tribological performance of the BN composite lubricants is attributed to the synergistic effect between nano-Si particles or Al2O3 particles and layered nano-BN particles. This accelerates the formation of solid lubrication film composed of BN, Si, Al2O3, and Fe2O3 on the surface of the AlN plate, thus reducing the wear between friction pairs.