To significantly improve the tribological performance of epoxy resin (EP), a novel h-BN/MoS2 composite was successfully synthesized using spherical MoS2 particles with lamellar self-assembly generated through the calcination method, followed by utilizing the “bridging effect” of a silane coupling agent to achieve a uniform and vertically oriented decoration of hexagonal boron nitride (h-BN) nanosheets on the MoS2 surface. The chemical composition and microstructure of the h-BN/MoS2 composite were systematically investigated. Furthermore, the enhancement effect of composites with various contents on the frictional properties of epoxy coatings was studied, and the mechanism was elucidated. The results demonstrate that the uniform decoration of h-BN enhances the chemical stability of MoS2 in friction tests, and the MoS2 prevents oxidation and maintains its self-lubricating properties. Consequently, due to the protective effect of h-BN and the synergistic interaction between h-BN and MoS2, the 5 wt % h-BN/MoS2 composite exhibited the best friction and wear resistance when incorporated into EP. Compared to pure EP coatings, its average friction coefficient and specific wear rate (0.026 and 1.5 × 10−6 mm3 N−1 m−1, respectively) were significantly reduced. Specifically, the average friction coefficient decreased by 88% and the specific wear rate decreased by 99%, highlighting the superior performance of the h-BN/MoS2-enhanced epoxy composite coating.
