A new approach to prepare α-FeOOH/reduced graphene oxide (RGO) at room temperature has been developed. Instead of reducing graphene oxide (GO) with the most commonly used reagents, which are highly toxic or explosive, Fe²⁺ was used as the reducing reagent. Fe²⁺ efficiently reduced GO under mild conditions to form α-FeOOH/RGO via spontaneous in situ deposition of α-FeOOH nanorods onto the RGO surfaces. The resulting α-FeOOH/RGO was characterized by transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, x-ray photoelectron spectroscopy, x-ray diffraction analysis and infrared spectroscopy. The α-FeOOH/RGO was then applied as a photocatalyst for the degradation of the azo dye, methyl orange.