Pomelo, Citrus maxima, peel was chemically modified with lime water and then loaded with Fe(III) to develop anion exchange sites for effective sequestration of As(V) from water. Biosorbent characterizations were done by using FTIR, SEM, XRD, EDX, and Boehm's titration. The batch biosorption studies were carried out at various pHs using modified and non-modified biosorbents and optimum biosorption of As(V) occurred at acidic pH (3.0–5.0) for both the biosorbents. A kinetic study showed a fast biosorption rate and obtained results fitted well with the pseudo-second-order (PSO) model. When isotherm data were modeled using the Langmuir and Freundlich isotherm models, the Langmuir isotherm model fit the data better and produced maximal As(V) biosorption capacities of 0.72 ± 03, 0.86 ± 06, and 0.95 ± 05 mmol/g at temperatures 293± 1K, 298± 1K and 303± 1K, respectively. Desorptionof As(V) was effective using 0.1 M NaOH in batch mode. Negative values of ΔG° for all temperatures with positive ΔH° confirmed the spontaneous and endothermic nature of As(V) biosorption. The existence of co-existing chloride (Cl−), nitrate (NO3−), sodium (Na+), and calcium (Ca2+) showed insignificant interference whereas a high concentration of sulphate (SO42−) and phosphate (PO43−) significantly lowered As(V) biosorption percentage. Arsenic concentrations in actual arsenic polluted groundwater could be reduced to the WHO drinking water standard (10 μg/L) by using only 1 g/L of investigated Fe(III)-SPP. The dynamic biosorption of As(V) in a fixed bed system showed that Fe(III)-SPP was effective also in continuous mode and different design parameters for fixed bed system were determined using Thomas, Adams-Bohart, BDST, and Yoon-Nelson models. Therefore, from all of these results it is suggested that Fe(III)-SPP investigated in this study can be a potential, low cost and environmentally benign biosorbent material for an effective removal of trace amounts of arsenic from polluted water.