The electrospinning of polyvinyl alcohol (PVA) was performed with maleic anhydride (MA) as a cross linker to fabricate slightly soluble nanofiber membrane. The solubility, morphology and thermal behavior of electrospun PVA and PVA/MA membranes were characterized by water durability test, scanning electron microscope (SEM) and differential scanning calorimeter (DSC), respectively. Water durability test demonstrated that 8% PVA/MA (20/1, mole/mole) membrane had the least average mass loss and standard deviation. SEM images showed that fibers in PVA/MA membrane had a larger average diameter compared to those in PVA membrane. DSC investigated that crystal structure was formed in PVA/MA membrane. The results show that rapid evaporation of water and high electric field during electrospinning process may promote crosslinking of PVA and MA. (C) 2008 Elsevier B.V. All rights reserved.