Electrospinning can prepare bio-scaffold materials that mimic extracellular matrix, and good biocompatibility can be obtained by using poly-caprolactone (PCL) as the raw material. The combination of PCL electrospun nanofibers with inorganic materials can improve the hydrophilic and mechanical properties of scaffold materials, regulate the degradation performance and enhance the biomineralization ability, which has good application promising applications. In this paper, we review the application of polycaprolactone electrospun nanofiber-based hybrid biomaterials in dentistry.