One-dimensional Zn-doped α-Fe2O3 nanowires have been controllably synthesized by using the pure pyrite as the source of Fe element through a two-step synthesis route, including the preparation of Fe source solution by a leaching process and the thermal conversion of the precursor solution into α-Fe2O3 nanowires by the hydrothermal and calcination process. The microstructure, morphology, and surface composition of the obtained products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was found that the formation process of α-Fe2O3 is significantly influenced by the introduction of Zn2+. The gas sensing measurements indicated that the sensor based on 1% Zn-doped α-Fe2O3 nanowires showed excellent H2S sensing properties at the optimum operating temperature of 175 °C. Notably, the sensor showed a low H2S detection limit of 50 ppb with a sensor response of 1.5. Such high-performance sensing would be ascribed to the one-dimensional structure and high specific surface area of the prepared 1% Zn-doped α-Fe2O3 nanowires, which can not only provide a large number of surface active sites for the adsorption and reaction of the oxygen and H2S molecules, but also facilitate the diffusion of the gas molecules towards the entire sensing materials.