We report a ZnO/Silicon nanowire (ZnO/Si NWs) heterojunction array-based NO gas sensor operating at room temperature with an extremely high response (noise limited response ∼10 ppb). The sensor shows very high selectivity towards NO gas sensing and limited perturbation in response due to the presence of moisture. The sensor has been fabricated by using cost-effective chemical processing that is compatible with wafer-level processing. The vertically aligned Si NWs array has been made by an electroless etching method and the ZnO nanostructure was made by chemical solution deposition and spin-coating. Extensive cross-sectional electron microscopy and composition analysis by line EDS allowed us to make a physical model. The electrical characteristic of the model was to fit the I-V data before and after exposure to gas and essential changes in electrical parameters were obtained. This was then explained based on a proposal for the mechanism of gas sensing. We observe that the heterostructure leads to a synergetic effect where the sensing response is more than the sum total of the individual components, namely the ZnO and the Si NWs. The response is much enhanced in the p-n junction when the n-ZnO nanostructure interfaces with p-Si NW compared to that in the n-n junction formed by ZnO on n-Si NW.