In the present study, electrospun nanofiber membranes (ENMs) of polyacrylonitrile (PAN) were modified by dispersing α-Fe2O3 nanoparticles, synthesized using a thermal solvent process, in a PAN solution. The morphology and physiochemical properties of the prepared ENMs and the α-Fe2O3 were characterized using FESEM, EDX, BET, XRD, FTIR, porosity, and contact angle measurement. XPS was used to investigate the interaction of ENM with arsenate (As(V)) during the adsorption. Moreover, the effect of pH, the equilibrium isotherm, and the kinetics were investigated in batch experiments. The Langmuir isotherm best correlated the experimental results, indicating monolayer adsorption on ENMs, and the kinetics was best fitted, R2 > 0.99, by the pseudo-second-order model. In addition, the effects of certain conditions on the filtration performance were examined, such as feed concentration and transmembrane pressure (TMP). By passing sodium hydroxide (0.1 M) for 20 min, the membrane was regenerated. The increase in TMP, along with the presence of co-ions including chloride, nitrate, and sulfate, had negative impacts on the removal of As(V). The results show that the modified ENMs with α-Fe2O3 nanoparticles are applicable for As(V) ion removal and possibly for eliminating other heavy metals from aqueous media.