Some special advantages of poly vinyl alcohol (PVA), including biocompatibility and non-toxicity, make it a good choice to be used in drug delivery systems. The large swelling capacity of PVA requires to be adequately stabilized to ensure that carriers could be retained in water. Thus, to form electrospun fibers and improve stability in aqueous mediums, PVA is often exposed to a stabilization process. In this work, PVA/sodium alginate (SA) nanofibers with core/shell structure were fabricated by electrospinning of PVA (10 w/v%) and SA (2 w/v%) in water. The electrospun nanofibers were characterized using scanning electron microscopy, transmission electron microscopy, thermal gravimetric analysis, differential scanning calorimetry and Fourier transform infrared spectrometry. These characterizations showed that there were good interactions between PVA and SA caused by probable hydrogen bonds. In vitro tests exhibited that the core/shell structure of PVA/SA nanofibers could be regarded as a suitable carrier for the controlled release delivery of dexpanthenol (delivery for 150 h), as well it was indicated that the drug release from dexpanthenol-loaded nanofibers follows Korsmeyer-Peppas model with Fickian diffusion mechanism. [ABSTRACT FROM AUTHOR]