In this study, we devised a novel nanofibrous adsorbent made of polyethersulfone (PES) for removal of methylene blue (MB) dye pollutant from water. The polymer shows a low isoelectric point thus at elevated pHs and, being nanofibrous, can offer a huge highly hydroxylated surface area for adsorption of cationic MB molecules. As an extra challenge, to augment the adsorbent’s properties in terms of adsorption capacity in neutral and acidic conditions and thermal stability, vanadium pentoxide (V2O5) nanoparticles were added to the nanofibers. Adsorption data were analyzed according to the Freundlich adsorption model. The thermodynamic parameters verified that only at basic pH is the adsorption spontaneous and in general the process is entropy-driven and endothermic. The kinetics of the adsorption process was evaluated by the pseudo-first- and pseudo-second-order models. The latter model exhibited the highest correlation with data. In sum, the adsorbent showed a promising potential for dye removal from industrial dyeing wastewater systems, especially when envisaging their alkaline and hot conditions.