In this study, wound dressings consisting of dexpanthenol (Dex)-loaded electrospun nanofibers were fabricated using polyvinyl alcohol (PVA)/ sodium alginate (SA), and chitosan as the core and the shell, respectively. Considering the remarkable properties of chitosan, it was used as a shell against drug release and to improve the thermal stability, and tensile strength of the scaffold. By comparing the thermogravimetric, and tensile strength results of nanofibers with and without shell, it was revealed that the presence of chitosan in the shell side could improve the thermal stability and increased the tensile strength by about three times. The isotherm models of dexpanthenol release from the PVA/SA/Dex-CS scaffold was best described by the Langmuir model. Besides, Fourier transform infrared, scanning electron microscopy, and X-ray diffraction techniques were performed to characterize nanofibers. Furthermore, an in vivo investigation of a wound dressing with dexpanthenol showed better healing compared to the wound dressings without dexpanthenol.