The dye production and its use in textile and related industries resulted in discharge of dye to wastewater. Adsorption for color removal is known as equilibrium separation process, and the resultant decolorization is influenced by physicochemical factors such as adsorbent surface area. The nanofiber membranes prepared by the electrospinning method have controllable nanofiber diameter and pore size distribution (PSD) with a high surface area to volume or mass ratio. In this study, polyvinyl alcohol (PVA) nanofibrous membranes were prepared by the electrospinning method at different collection times such as 3, 5 and 10 h and heat fixated at 130, 150 and 170°C for 10 min, and then, the adsorption capability of PVA nanofiber membranes for Reactive Red 141 from aqueous solution was investigated. In order to make PVA nanofibers stable to water, the nanofibrous membranes were chemically cross-linked by a polycarboxylic acid (1,2,3,4 butanetetracarboxylic acid (BTCA)). PVA nanofibrous membranes were characterized by scanning electron microscopy, thermogravimetric analysis, swelling tests and pore size analysis. The results indicated that BTCA crosslinking improved the thermal and water stability of the nanofibrous structure but has no significant effect on the pore sizes of the membranes. Adsorption of Reactive Red 141 was studied by the batch technique, and it was observed that PVA nanofibers removed approximately >80% of the dye.