Ultrathin CeO₂ nanowires with a diameter of 5 nm and an aspect ratio of more than 100 can be prepared by a one-step refluxing approach in a mixed solvent composed of water and ethanol without using any templates or surfactants. The formation mechanism of the as-synthesized ultrathin nanowires has been investigated. The as-synthesized CeO₂ nanowires with a high surface area of 125.31 m² g⁻¹ exhibited excellent wastewater treatment performance with high removal capacities towards organic dyes and heavy metal ions. In addition, the as-synthesized CeO₂ nanowires can adsorb Congo red selectively from a mixed solution composed of several dyes. Successful access to high quality ultrathin nanowires will make it possible for their potential application in catalysis and other fields.