The present study reports green electrospinning of polyvinyl alcohol (PVA) / citric acid nanofiber membranes, and the membranes were then crosslinked by heat treatment. The electric conductivity of the PVA aqueous solution increases rapidly and the growth slows down along with the increase of citric acid content. The viscosity of 13 wt% PVA aqueous solutions with citric acid had a small increase and remained stable in one week, which was suitable for electrospinning fibers. Porous, interconnected nonwoven nanofiber membranes were electrospun from a thoroughly mixing of PVA/citric acid aqueous solution. The membranes were then heat treated at 140 degrees C for 2 h. The postelectrospinning crosslinked nanofiber membranes were insoluble in water, while the non-crosslinked electrospun nanofiber membranes dissolved instantaneously. FT-IR spectrum, X-ray diffraction, and DSC thermograms reveal that crosslinking of PVA nanofiber membranes occurred through esterfication reaction during heat treatment.