Fe (III)-loaded chitosan (CS) hollow fibers (CS-Fe (III) HF) were successfully prepared according to the dry-wet spinning technique. The CS-Fe (III) HFs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and thermal gravimetric analysis (TGA). Removal of pentavalent arsenic was studied through biosorption on CS-Fe (III) HF adsorptive membranes. The response surface methodology (RSM) was applied to investigate the influence of the main operating parameters such as contact time, pH, initial As (V) concentration and HFs dosage on the adsorption capacity of As (V). From the Pareto analysis, pH, [As (V)]o, [CS-Fe (III) HF membranes] and squared effect of [As(V)]o were found to produce the largest effect on biosorption of As (V). Kinetic studies showed that the pseudo-second-order kinetic model provides the best correlation to the experimental results. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 3,703 μg g−1. A laboratory scale glass membrane module consisting of three CS-Fe(III) HFs has also been prepared and tested for biosorption of As (V) at a real scale. Permeability of As (V) ions through the CS-Fe (III) HF membranes was 0.145 μmol m−2 h−1 bar −1.