Sn-doped ZnO and pure ZnO thin films are deposited on glass substrates with prepared electrode by the chemical vapor deposition method. The gas sensing performances of Sn-doped ZnO and pure ZnO thin films are investigated by our home-made system at room temperature, and the gas sensing test results reveal that Sn-doped ZnO thin film exhibits high gas response to ethanol and acetone, while no response is detected for pure ZnO to ethanol or acetone at room temperature. Sn-doped ZnO thin film also has high selectivity that the response to ethanol is higher than that to acetone in the same measurement conditions, and the response of Sn-doped ZnO thin film sample to ethanol is almost the third largest when the concentration is 320 ppm. The typical scanning electron microscopy images reveal that these two samples are tetrapod-shaped ZnO whiskers with diameters in a range of about 150-400 nm. X-ray diffraction results indicate that all the samples are of wurtzite structure. Neither trace of Sn, nor that of Sn alloy nor that of Sn oxide is detected in the Sn-doped ZnO film, while its diffraction peak shifts towards the left compared with that of pure ZnO sample, which suggests that Sn atoms exist in the form of interstitial atoms in the ZnO crystal. The energy dispersive spectrum shows that the Sn-doped ZnO thin film is composed of Zn and O elements, and no Sn signal is defected. Photoluminescence spectra reveal that both Sn-doped ZnO and pure ZnO films have ultraviolet light emission peaks and green emission peaks, while the intensities of the defect emissions are significantly enhanced by doping of Sn. In addition, no gas response to ethanol is detected after Sn-doped ZnO thin film has been annealed in the air, which indicates that the room temperature gas sensitivity of the Sn-doped ZnO thin film may be related to its high defect concentration. The working mechanism of Sn-doped ZnO thin film is explained by a free electron random scattering model. As is well known, ZnO semiconductor gas-sensor is of surface-controlled type. In this work, upon exposure to ethanol vapor, the physical absorbed ethanol molecules acting as scattering centers can reduce the mean free path of the electrons in the surface of the film, changing the mean free time n, which would increase the resistance of Sn-doped ZnO thin film at room temperature. This work provides a simple method of fabricating the highly sensitive ethanol gas sensor operating at room temperature, which has great potential applications in gas sensor field.