The rapid advancement of communication technology has substantially increased the demand for advanced electronic packaging materials with high thermal conductivity and outstanding electrical insulation properties. In this study, we design polyvinyl alcohol/polydopamine-modified boron nitride nanosheet (PVA/BNNS@PDA) nanocomposites with hierarchical structures by combining electrospinning, vacuum filtration deposition, and hot pressing. The modified BNNS@PDA improves the interaction between the filler and the polymer matrix while reducing the interfacial thermal resistance, resulting in superior thermal conductivity, excellent insulation, and perfect flexibility. The PVA/BNNS@PDA nanocomposites possess an ultrahigh in-plane thermal conductivity of 16.6 W/(m·K) at 35.54 wt % BNNS@PDA content. Even after 2000 folds, the nanocomposites do not undergo any crack, showing their ultrahigh thermal conductivity behavior. Furthermore, the nanocomposites exhibit a volume resistivity above 10 14 Ω·cm, which is well above the standard for insulating materials. Based on these results, this work provides a novel method to produce nanocomposites with high thermal conductivity, offering a new perspective to design advanced thermal management materials.