Zinc hydroxyfluoride (ZnOHF) is a newly found resistive semiconductor used as a gas-sensing material with excellent selectivity to NO2because of its unique energy band structure. In this paper, Al3+doping and UV radiation were used to further improve the gas-sensing performance of ZnOHF. The optimized 0.5 at.% Al-ZnOHF sample exhibits improved sensitivity to 10 ppm NO2at a lower temperature (100 °C) under UV assistance, as well as a short response/recovery time (35 s/96 s). The gas-sensing mechanism demonstrates that Al3+doping increases electron concentration and promotes electron transfer of the nanorods by reducing the bandgap of ZnOHF, and the photogenerated electrons and holes with high activity under UV irradiation provide new reaction routes in the gas adsorption and desorption process, effectively promoting the gas-sensing process. The synergistic effect of Al3+and UV radiation contribute to the enhanced performance of Al-ZnOHF.