The thermal management problem in the field of electronic components is becoming more and more serious, the use of boron nitride modified polymer matrix to produce thermally conductive composites has become one of the popular explorations at present and in order to prepare new materials for application in high thermal conductivity insulation sites. The introduction of boron nitride nanomaterials with high thermal conductivity can not only solve the problem of low thermal conductivity of polymer materials, but also improve the mechanical properties, electrical insulation properties, and thermal stability of the produced boron nitride modified polymer thermal conductivity composites. This paper briefly introduced the structural properties and various preparation methods of boron nitride, and reviewed the modification of polymer materials with hexagonal boron nitride from three aspects: functionalization, orientation dispersion, and three-dimensional network construction, as well as the synergistic hybridization of hexagonal boron nitride and zero- dimensional, one- dimensional, and multidimensional thermally conductive filler polymer materials in conjunction with the research work of the group. Finally, the main problems of hexagonal boron nitride modified polymeric thermally conductive composites at present stage were presented, and the future research directions were analyzed and prospected.