Starch is an attractive polymer for wound healing applications because of its wide availability, low cost, biocompatibility, biodegradability and wound-healing property. Here, we have fabricated starch-based nanofibrous scaffolds by electrospinning for wound healing applications. The diameter of the optimized nanofibers was determined by field emission scanning electron microscopy (FE-SEM) and was found to be in the range of 110–300 nm. The mechanical strength (0.5–0.8 MPa) of the nanofibrous scaffolds was attuned using polyvinyl alcohol (plasticizer) and glutaraldehyde (crosslinking agent), to impart them with sufficient durability for skin tissue engineering. Absence of negative interactions between the polymers was confirmed by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), differential scanning microscopy (DSC) and thermal gravimetric analysis (TGA). Cellular assays with L929 mouse fibroblast cells indicated the ability of the scaffolds to promote cellular proliferation, without exhibiting any toxic effect to the cells. Thus, the nanofibrous scaffolds demonstrated potential for wound healing applications.