The aim of this study was to prepare and characterize electrospun polyvinyl alcohol (PVA) nanofiber mats loaded with capsaicin (CC) as a transdermal drug delivery system. The amount of CC loaded in the base PVA solution (10 %w/v solution) was 0.025, 0.0375 and 0.05 %, based on the dry weight of PVA (% wt). The average diameters of these fibers ranged from 121 to 165 nm. In all concentrations of CC loaded in spun PVA fiber mats, an amorphous nanodispersion of CC with PVA was obtained. The tensile strength of the as-spun fiber mats was lower than that of the as-cast PVA films. The release rate of CC from CC-loaded as-spun PVA was significantly higher than from CC-loaded as-cast PVA films, and increased when the CC content in both CC-loaded as-spun PVA and CC-loaded as-cast PVA films increased. Our research suggests a potential use for CC-loaded electrospun PVA mats as a transdermal drug delivery system.