In order to search for catalysts with high catalytic activity, environmental friendliness, low price, and good stability, and to investigate the synergistic catalytic effect between metals and supports, porous h-BN carriers with a large specific surface area, meanwhile rich in hydroxyl and amino groups on the surface, were prepared by the calcined precursor method. Cu/BN nanocomposites with uniform particle size distribution were successfully prepared by a simple liquid phase reduction method. The composition, microstructure and properties of the composites were characterized. The results show that the introduction of Cu NPs does not destroy the two-dimensional sheets structure of porous h-BN, but the specific surface area and pore size decrease to varying degrees. Through investigating the catalytic performance of Cu/h-BN composite materials by using the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model reaction, it shows that when the Cu NPs content is 6% (mass fraction), the Cu/h-BN composite material exhibits the best catalytic activity (the reaction rate constant k= 4.62×10-2 s-1) and stability, and the catalytic activity remains unchanged in five cycles. Therefore, the h-BN carrier with a high specific surface area can stabilize Cu nanoparticles, and the synergistic catalytic effect between them enables Cu/h-BN to have excellent catalytic activity and stability. The study provides a theoretical basis for further research on the synergistic catalysis of metals and h-BN in the future.