Thermal conductivity was dramatically increased after adding natural fiber into hexagonal boron nitride (hBN)/epoxy composites. Although natural fiber does not show high-thermal conductivity itself, this study found that the synergy of natural fiber with hBN could significantly improve thermal conductivity, compared with that solely using hBN. A design of mixtures approach using constant fibers with increasing volume fractions of hBN was examined and compared. The thermal conductivity of the composite containing 43.6% hBN, 26.3% kenaf fiber and 30.1% epoxy reached 6.418 W m⁻¹ K⁻¹, which was 72.3% higher than that (3.600 W m⁻¹ K⁻¹) of the 69.0% hBN and 31.0% epoxy composite. Using the scanning electron microscope (SEM) and micro computed tomography (micro-CT), it was observed that the hBN powders were well distributed and ordered on the fiber surfaces enhancing the ceramic filler’s interconnection, which may be the reason for the increase in thermal conductivity. Additionally, the results from mechanical and dynamic mechanical tests showed that performances dramatically improved after adding kenaf fibers into the hBN/epoxy composite, potentially benefiting the composite’s use as an engineered material.