With the rapid development of 5G information technology, thermal conductivity/dissipation problems of highly integrated electronic devices and electrical equipment are becoming prominent. In this work, “high-temperature solid-phase & diazonium salt decomposition” method is carried out to prepare benzidine-functionalized boron nitride (m-BN). Subsequently, m-BN/poly(p-phenylene benzobisoxazole) nanofiber (PNF) nanocomposite paper with nacre-mimetic layered structures is prepared via sol–gel film transformation approach. The obtained m-BN/PNF nanocomposite paper with 50 wt% m-BN presents excellent thermal conductivity, incredible electrical insulation, outstanding mechanical properties and thermal stability, due to the construction of extensive hydrogen bonds and π–π interactions between m-BN and PNF, and stable nacre-mimetic layered structures. Its λ∥ and λ⊥ are 9.68 and 0.84 W m-1 K-1, and the volume resistivity and breakdown strength are as high as 2.3 × 1015 Ω cm and 324.2 kV mm-1, respectively. Besides, it also presents extremely high tensile strength of 193.6 MPa and thermal decomposition temperature of 640 °C, showing a broad application prospect in high-end thermal management fields such as electronic devices and electrical equipment.