Hexagonal boron nitride (h-BN) is commonly used as a polymer filler to produce wearables with outstanding heat dissipation properties and excellent biocompatibility. However, the poor interfacial compatibility of h-BN in polymers, resulting from the chemical inertness of boron nitride and the low stripping efficiency of h-BN, limits its performance in thermal conductivity (TC) applications. To address these issues, we innovatively introduced a solid-phase molten salt method combined with a hydrothermal exfoliation strategy in this work to obtain poly(Nvinyl-2-pyrrolidone) stabilized hydrophilic boron nitride nanosheets (p-BNNSs). Notably, the method is simple and efficient, and the prepared p-BNNSs have fewer layers and higher hydrophilicity. The TC of the 30 wt % p-BNNSs@PVA films reached 7.38 W m −1 K −1 , representing a 3244% enhancement compared to pure PVA films. The nanofiber film was fabricated using electrospinning with the optimal filling ratio, successfully facilitating heat conduction on human skin. Finally, it is proposed that the use of nanofiber films as advanced medical films offers a practical solution to the negative impact of hot weather on wound healing.