In order to prepare a dry mask and solve the problem of using preservatives and thickeners in wet mask to prolong the shelf life of mask and cause damage to skin, double-layer nanofiber films with polyvinyl alcohol (PVA), silk protein (SF) loaded with Cortex fraxini (CRF) as "skin-friendly layer" and polycaprolactone (PCL) as hydrophobic layer were prepared by sequential electrostatic spinning technology. The films were characterized by scanning electron microscopy, infrared spectroscopy and water contact angle, and their adhesion, release, antioxidant and biocompatibility properties were investigated. The results show that PVA/SF can be loaded with different concentrations of CRF at 1%, 3% and 5%, and the PVA/SF/CRF-PCL fiber membranes have strong adhesion after wetting, while CRF can reach the release equilibrium at about 4 min to achieve rapid release. The PVA/SF fibrous membrane loaded with 5% CRF has good antioxidant properties, and the scavenging rates of DPPH radicals and ABTS radicals are 89.13%±0.42% and 85.49%±0.82%, respectively. The PVA/SF/CRF-PCL fibrous membrane has a low hemolysis rate and is not toxic to B16 cells and Hela cells, and the survival rate of B16 cells is 89% or more, showing a good biocompatibility and can be safely applied in the skin field.