Hexagonal boron nitride (h-BN) has recently gained much attention due to its high thermal conductivity and low electrical conductivity. In this study, we proposed to evaluate the impact of the modification of h-BN for use in a polymethylmethacrylate/polyamide 6 (PMMA/PA6) polymer blend. Different methods to modify h-BN particles and improve their affinity with polymers were proposed. The modification was performed in two steps: (1) a hydroxylation step for which three different routes were used: calcination, acidic treatment, and ball milling using gallic acid; (2) a grafting step for which four different silane agents were used, carrying different molecular or macromolecular groups: the octadecyl group (Si-C18), propyl amine group (Si-NH2), polystyrene chain (Si-PS), and PMMA chain (Si-PMMA). The modified h-BN samples after hydroxylation and functionalization were characterized by FTIR and TGA. Py-GC/MS was also used to prove the successful graft with Si-C18 groups. Sedimentation tests and multiple light scattering were performed to assess the surface modification of h-BN. Granulometry and SEM observations were performed to evaluate the particle size distribution after hydroxylation. After the addition of Si-PMMA modified h-BN into a PMMA/PA6 co-continuous blend, the morphology of the polymer blend nanocomposites was characterized using SEM. The calculation of the wetting parameter based on the surface tension measurement using the liquid drop model showed that h-BN dispersed in the PA6 phase. Grafting PMMA chains onto hydroxylated h-BN particles combined with an adequate sequence mixing led to a successful localization of the grafted h-BN particles at the interface of the PMMA/PA6 blend.