The effects of rare earth elements (Ce, Eu, and Er) doping on the microstructure and gas sensing properties of ZnO nanowires were investigated. The Ce, Eu, Er-doped ZnO nanowires and pristine ZnO nanowires were synthesized via a solvothermal route. The structure of the prepared samples was studied and compared by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron microscopy. The gas sensors were fabricated by coating the prepared samples on aluminum oxides tube-based Au sensing electrode, with Ni-Cr heating wire to control the operating temperature. The operating temperature of all sensors was determined to be 300 °C with consideration of ethanol response. At this temperature, all sensors showed good ethanol sensing performance, with the 1%Ce-doped ZnO nanowires-based sensor exhibited the highest ethanol response over the other sensors. The mechanism for the microstructure and gas sensing behavior difference of various samples was discussed.