Polyamide 6/boron nitride (PA6/BN) composites were synthesized via anionic ring-opening polymerization using epsilon-caprolactam as the monomer and functional boron nitride (f-BN) as the thermal conductive filler. Besides the homopolymerized PA6, some PA6 molecule chains would grow from the f-BN sheets through the "grafting from" strategy. Compared with unfunctional hexagonal BN (h-BN), the introduction of f-BN not only improved the dispersion of f-BN in the matrix but also enhanced the interface bonding between f-BN and PA6. The homogeneous dispersion of f-BN in the PA6/f-BN composite favored the formation of the continuous thermal conductive paths or network at a low f-BN loading, and the good interface bonding reduced the phonon scattering in the interface, which improved the thermal conductivity (TC) of the PA6/f-BN composite by 66.0% compared with that of the pure PA6, when only 5 wt% f-BN was added. In contrast, with the same content of unfunctional h-BN loading, the TC of the corresponding composite merely improved by 29.7%. Moreover, Young's modulus and yield strength of PA6/f-BN composites had increased obviously with the introduction of f-BN, whereas those of PA6/h-BN composites showed small fluctuation with the same contents of BN. POLYM. ENG. SCI., 2020. (c) 2020 Society of Plastics Engineers