Chitosan-polyvinyl alcohol (PVA) blend nanofibrous webs were fabricated in different blend ratios through electrospinning procedures. From scanning electron microscopy (SEM) results, 25/75 blend ratio of chitosan-PVA was selected for biological studies. In vivo studies were carried out on the dorsum of rats of two types: longitudinal incisional wounds (n = 8 rats) and round excisional wounds (n = 8). Pathological study was done on the wounds to investigate the healing process. The histological study in wound healing indicated that the administration of chitosan nanofibrous web improved the wound healing, qualitatively and quantitatively.