The rapid development of 5G equipment and high-power density electronic devices calls for high thermal conductivity materials for heat dissipation. Dielectric polymer composites are highly promising as the electrical insulation, mechanical property, thermal stability, and even fire retardance are also of great importance for electrical and electronic applications. However, the current thermal conductivity enhancement of dielectric polymer composites is usually at the cost of lowering the mechanical and electrical insulating properties. In this work, we report the facile preparation of highly thermally conductive and electrically insulating poly­(p-phenylene benzobisoxazole) nanofiber (PBONF) composites by incorporating a low weight fraction of functionalized boron nitride nanosheets (BNNSs). With strong electrostatic interaction, the BNNSs are encapsulated by PBONFs, and the constructed robust interconnected network makes the nanocomposites exhibit a nacre-like structure. Accordingly, the nanocomposite paper has a high in-plane thermal conductivity of 21.34 W m–1 K–1 at a low loading of 10 wt % BNNSs and exhibits an ultrahigh strength of 206 MPa. Additionally, the nanocomposite paper exhibits superior electrical insulation properties up to higher than 350 °C and excellent fire retardance. The strong heat dissipation capability of the nanocomposite paper was demonstrated in 5G base stations and control transformers, showing wide potential applications in high power density electrical equipment and electronic devices.