A PVA nanofibrous matrix was prepared by electrospinning an aqueous 10 wt % PVA solution. The mean diameter of the PVA nanofibers electrospun from the PVA aqueous solution was 240 nm. The water resistance of the as-spun PVA nanofibrous matrix was improved by physically crosslinking the PVA nanofibers by heat treatment at 150 degrees C for 10 min, which were found to be the optimal heat treatment conditions determined from chemical and morphological considerations. In addition, the heat-treated PVA (H-PVA) nanofibrous matrix was coated with a chitosan solution to construct biomimetic nanofibrous wound dressings. The chitosan-coated PVA (C-PVA) nanofibrous matrix showed less hydrophilic and better tensile properties than the H-PVA nanofibrous matrix. The effect of the chitosan coating on open wound healing in a mouse was examined. The C-PVA and H-PVA nanofibrous matrices showed faster wound healing than the control. The histological examination and mechanical stability revealed the C-PVA nanofibrous matrix to be more effective as a wound-healing accelerator in the early stages of wound healing than the H-PVA nanofibrous matrix.