Electrospun nanofibrous hydrogel membranes have been gaining significant importance due to the combination of unique physical properties of nanofibers and biocompatibility of hydrogels. Thus, they are considered as potential candidates for medical textile applications. This study deals with electrospinning of poly(vinyl alcohol) (PVA) hydrogel nanofibrous membranes. The chemical crosslinking of PVA with proportionate quantities of 1,2,3,4 butanetetracarboxylic acid (BTCA) was undertaken to form hydrogel structures. Cross-linked membranes were characterized by scanning electron microscopy, FT-IR and thermogravimetric analysis, water swelling, and durability tests. FT-IR analysis demonstrated the formation of ester linkages between PVA and BTCA and thermogravimetric analysis showed that crosslinking improved the thermal stability of the nanofibrous structure. Furthermore, the results indicated that crosslinking with BTCA improved water stability of PVA membranes and the nanofibrous structure was preserved after water treatment. It is envisaged that use of BTCA as a cross-linker to form hydrogel nanofibers could be a practical and a promising method for medical textile applications, especially for wound dressings given its nontoxicity and immiscibility with polymer solutions. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013