AbstractEstablishing a robust interfacial bond between hexagonal boron nitride (h‐BN) plates and the epoxy matrix is essential for enhancing heat transfer, which is difficult because of h‐BN's low‐surface energy, tendency to clump together, and the chemical inertness of the epoxy matrix. This research shows different techniques for treating the surface of h‐BN fillers by applying acids and thermal processes to activate the surface. The silanization process was used to increase the silane content on the surface of activated h‐BN in order to make it more compatible with the epoxy matrix. X‐ray photoelectron spectroscopy analysis revealed silicon peaks (Si2s peak at 150.1 eV and Si2p peak at 100.3 eV) in the spectrum of silane‐treated samples. Heat treatment resulted in the production of more oxygen molecules on the shell of h‐BN compared to the acid treatment. Here, the primary focus was on examining how surface treatment affects thermal conductivity (TC) performance in both in‐plane and through‐thickness paths. There was an increase in the epoxy's TC perpendicular to the plane, going from 0.21 to 0.47 (W/mK), showing a remarkable 123.8% enhancement by adding 10 wt% of silane‐modified‐thermal treated h‐BN particles. The improvement resulted from effectively silanizing the exterior boundary of h‐BN particles, enhancing connection and distribution in the epoxy matrix. Surface modification of h‐BN‐epoxy composites improves TC, leading to better heat conduction in thermal management systems, benefiting industries like aerospace, automotive, and energy systems.Highlights Silanization of h‐BN for better filler‐matrix bonding leading to improved heat transfer Boosting thermal conductivity in the through‐thickness direction with surface‐modified h‐BN Significant improvement in through‐thickness thermal conductivity with treated h‐BN. Thermal treatment of h‐BN produced better oxygenation than acid treatment. Application in aerospace and automotive through improved heat transfer.