A novel iron-doped chitosan electrospun nanofiber mat (Fe@CTS ENM) was synthesized, which was proven to be effective for the removal of arsenite (As(III)) from water at neutral pH condition. The physiochemical properties and adsorption mechanism were explored by SEM-EDS and X-ray photoelectron spectroscopy (XPS). Batch adsorption experiments were carried out to evaluate the As(III) adsorption performance of the Fe@CTS ENM with various process parameters, such as adsorbent dose, solution pH, initial As(III) concentration, contact time, ionic strength, coexisting anions, and natural organic matter. The experimental results indicated that the maximum adsorption capacity was up to 36.1 mg g^-1. Especially, when the adsorbent dosage was higher than 0.3 g L^-1, the As(III) concentration was reduced from 100 μg L^-1 to less than 10 μg L^-1, which indicated the Fe@CTS ENM could effectively remove trace As(III) from water over a wide pH range (from 3.3 to 7.5). Kinetics study demonstrated that the adsorption equilibrium was achieved within 2.0 h, corresponding to a fast uptake of As(III). The presence of common co-ions and humic acid had little effect on the As(III) adsorption. XPS analysis suggested that the FeO, COH, COC and CN groups on the adsorbent surface play dominant roles in the adsorption of As(III). Adsorption-desorption regeneration test further demonstrated that no appreciable loss in the adsorption capacities was observed, which confirmed that the Fe@CTS ENM maintained a desirable life cycle that was free of complex synthesis processes, expensive and toxic materials, qualifying it as an efficient and low-cost As(III) adsorbent.