Many efforts had been reported to modify the structure of electropun nanofibers in order to obtain superior functional properties of poly(vinyl-alcohol) (PVA). This paper discusses the influence of chitosan on the morphology of electropun PVA nanofibers and their related properties. Spider–net and fiber–bridging structured PVA nanofibers are successfully fabricated by blending with chitosan. Chitosan as natural cationic polysaccharide increases the excess charge of the host polymer PVA. Nanofibers are diverged into thinner nanofibers and a continuous web formed when electrical voltage applied. The presence of additional OH- groups from chitosan and larger surface area of the net structure for hydrogen bonding enhance the hydrophilicity and mechanical properties of the nanofiber mat as compare to pure PVA which are evaluated through water contact angle and tensile testing respectively.