Electrospinning is a simple, effective method for nanofiber nanofabrication using polymers. Poly(vinyl alcohol) (PVA) is a water-soluble and nontoxic polymer with good chemical and thermal stability. Electrospun PVA nanofibrous non-woven fabrics are expected to have significant applications in the area of membranes for filtration and biomedical engineering and protective clothes, etc. Stable electrospinning of PVA aqueous solution, however, was hampered by surface solidification causing splashing of the droplet. In this study, PVA nanofiber was continuously produced using coaxial electrospinning where PVA solution in the core was covered by poly(ethylene oxide) solution in the sheath preventing PVA surface drying. The effects of molecular weight and degree of hydrolysis on the morphology of electrospun PVA nanofiber were investigated. Also, PVA nanofiber was chemically cross-linked using poly(acrylic acid) (PAA) to improve its water resistance and avoid discoloration.