In this study, the synergistic effect of hexagonal boron nitride (h-BN) with cubic boron nitride (c-BN) on enhancement of thermal conductivity of epoxy resin composites has been reported. The measured thermal conductivities of the epoxy composites filled with h-BN, c-BN and hybrid h-BN/c-BN compared with the theoretical predications of Agari's model strongly suggest that the combination of h-BN platelets and c-BN spherical particles with different sizes is beneficial to enhance the thermal conductivity of the polymer composites by preferentially forming 3D thermally conductive networks at low loading content. Furthermore, the small addition of gold nanoparticles enhances the thermal conductivity from 166% to 237%. The potential application of these composites for thermal management has been demonstrated by the surface temperature variations in real time during heating. The results demonstrate that such thermally conductive but electrically insulating polymer-based composites are highly desirable for thermal management applications.