Polycrystalline ZnO nanowires with grain sizes ranging from 20 to 100 nm were synthesized using a newly designed two-step process: (first step) synthesis of ZnSe nanowires by vapor transportation of a mixture of ZnSe powders; and (second step) thermal oxidation of the ZnSe nanowires at 650 °C. Compared to the single-crystal ZnO nanowire gas sensors and other nanomaterial gas sensors reported previously, the multiple networked nanowire gas sensors fabricated from the nanograined ZnO nanowires showed substantially enhanced electrical responses to NO2 gas at 300 °C. The NO2 gas sensing properties of the nanograined ZnO nanowires increased dramatically with increasing NO2 concentration. The multiple-networked nanograined ZnO nanowire sensor showed a response value of 237,263% at 10 ppm NO2 and 300 °C, whereas the single-crystal ZnO nanowire sensors showed a response of only 6.5% under the same conditions. The recovery time of the nanograined ZnO nanowire sensor was much shorter than that of the normal ZnO nanowire sensor over the NO2 concentration range of 1-10 ppm, even though the response time of the former was somewhat longer than that of the latter. The origin of the enhanced NO2 gas sensing properties of the nanograined ZnO nanowire sensor is discussed.