The study investigates the production of ZnO nanorods and Polyethylene glycol (PEG) based ZnO nanorods for NO gas sensing applications influenced by temperature. ZnO nanorods were created using the hydrothermal method and then doped with PEG using the chemical stirring method. The sensors were characterized using Field emission scanning electron microscopy (FESEM), Grazing Incidence X-ray spectroscopy (GIXRD), and photoluminescence (PL) spectroscopy to assess their structural, morphological, and optical characteristics. The electrical conductivity and gas sensing properties of the nanoparticles were examined within a temperature range of 50–300 °C. Gas sensitivity was observed across the specified temperature range for various hazardous gases, including carbon monoxide, ethane, ammonia, and nitric oxide. The ZnO-PEG nanofilms exhibited a notably superior response to NO compared to the pristine ZnO nanorods. Nanostructured metal oxides with a high surface area allow for increased interaction with target gases, resulting in a significant increase in electrical resistance upon exposure. The sensor showed N-type semiconducting behavior in the presence of NO gas, showing the highest response of 230% at 200 °C, with extremely low response and recovery times of 6 s and 4 s respectively. The incorporation of PEG improves the gas-sensing properties of the nanorods because of surface modification.