Zigzag GaN/Ga2O3 heterogeneous nanowires (NWs) were fabricated, and the optical properties and NO gas sensing ability of the NWs were investigated. We find that NWs are most effective at 850 °C at a switching process once every 10 min (on/off = 10 min per each) with a mixture flow of NH3 and Ar. The red shift of the optical bandgap (0.66 eV) is observed from the UV-vis spectrum as the GaN phase forms. The gas sensing characteristics of the developed sensor are significantly replaced to those of other types of NO sensors reported in literature.