Coral-like and nanowire (NW) iron oxide nanostructures were produced at 700 and 800 °C, respectively, through thermal oxidation of iron foils in air- and water vapor-assisted conditions. Water vapor-assisted thermal oxidation at 800 °C for 2 h resulted in the formation of highly crystalline α-Fe2O3 NWs with good foil surface coverage, and we propose that their formation was due to a stress-driven surface diffusion mechanism. The Cr(VI) adsorption property of an aqueous solution on α-Fe2O3 NWs was also evaluated after a contact time of 90 min. The NWs had a removal efficiency of 97% in a 225 mg/L Cr(VI) solution (pH 2, 25 °C). The kinetic characteristic of the adsorption was fitted to a pseudo-second-order kinetic model, and isothermal studies indicated that the α-Fe2O3 NWs exhibited an adsorption capacity of 66.26 mg/g. We also investigated and postulated a mechanism of the Cr(VI) adsorption in an aqueous solution of α-Fe2O3 NWs.