Electrospun fibrous scaffolds are prepared from indigenously extracted and γ-irradiated blended chitosan (CS) with poly (vinyl alcohol) (PVA). The structure and morphology of the electrospun scaffolds are studied by FTIR spectroscopy and scanning electron microscopy (SEM). FTIR analyses verified the deacetylation of chitin and the developed interactions between chitosan and PVA. SEM images showed that bead on string fibers were obtained with high gamma rays dose due to the decrease in the molecular weight but no effect was observed on the size of the nanofibers. The cell cytotoxicity of the nanofibrous scaffolds was examined by indirect method using human fibroblast cells and human cancerous bone cells were employed for direct method. The evaluated results explained that CS/PVA electrospun scaffolds were compatible to the cells and can be employed for different biomedical applications.