Thermal behavior of electrospun PVA nanofibrous membranes was studied by thermal analysis techniques i.e., differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). For the production of nanofibrous membranes needleless (roller) electrospinning method was used. DSC graphs showed that there is a decrease in melting temperature of the PVA polymer when crosslinking agent is used. Moreover, the change in the polymer concentration doesn't influence the T-m. Considering the TGA results, it is realized that while crosslinked PVA nanofibers have weight losses at about 240 degrees C, pure PVA nanofibers have a weight loss at about 290 degrees C.