Arsenite (As(III)) and Selenate (Se(VI)) are universally touted as extremely toxic oxyanions in natural and industrial water systems. Thus, the production of low-cost adsorbents that are scalable and toxic-free is of great importance today. In this work, a large-scale goethite nanorods (α-FeOOH NRs) is synthesized using a modified rapid hydrolysis method. The obtained powder is characterized using different multidisciplinary techniques. Accordingly, the results showed uniform and straight nanorods (length ~400 nm and diameter ~40 nm) resembling cigar-like morphology while the structure is confirmed to be of orthorhombic α-FeOOH phase. The potential application of this material to adsorb As (III) and Se (VI) ions in water is explored. In particular, for initial adsorbate concentrations (~500 µg/L), the removal efficiencies are found exceptional with α-FeOOH doses of 0.33 g/L and ~0.5 g/L for As (III) and Se (VI), respectively. Attractively, the adsorption capacities were estimated using trusted isotherms and then experimentally verified at ultimately high concentrations. Besides, a pH-controlled adsorption study showed that a pH of 5–8 is a favored range for higher ionic uptake, which meets the World Health Organization (WHO) benchmarks of drinking water. To conclude, the α-FeOOH NRs are potential adsorbent for the sustainable removal of toxin ions in water systems.