In this study, we have synthesized alumina nanofibers by using an electrospinning method. The obtained alumina nanofibers were used as adsorbents for the removal of chromium(VI) and fluoride ions from an aqueous system. The morphology and size of the obtained nanofibers were characterized by scanning electron microscopy and transmission electron microscopy analytical techniques. The X-ray diffraction study of the nanofibers indicated the formation of pure and crystalline alpha-alumina. The effects of the pH, adsorbent dose, contact time, and initial concentration of the adsorbate on the alumina nanofiber surface have been studied. The optimum pH values for maximum removal of chromium(VI) and fluoride on the alumina nanofiber surface were found to be pH 5 and 7, respectively. The experimental data obtained from the adsorption studies by alumina nanofibers were analyzed by the Langmuir and Freundlich equation using a linearized correlation coefficient at room temperature. The Freundlich isotherm was found to fit well with the equilibrium data for adsorption of chromium(VI) and fluoride ions. The adsorption kinetics could be modeled by a pseudo-second-order rate expression. The maximum uptakes of chromium(VI) and fluoride by electrospun alumina nanofibers were found to be 6.8 and 1.2 mg/g, respectively.