Humidity is a key environmental parameter for VOCs detection technology. A study of the effects of humidity on both resolution and sensitivity of UV-FAIMS was performed at ambient temperature and pressure. This study was based on the detection and analysis of the differences in spectra (height, position and shape) and the α function of VOCs under different degrees of humidity. A total of three types of VOCs (ketones, alcohols and aromatics) were chosen as detection samples and a self-developed UV-FAIMS as a measurement instrument. The results show that sensitivity is inversely proportional to humidity for all VOCs. In addition, the resolution-humidity relationship exhibits strong dependence on the polarity of the sample ions. As relative humidity increased from 0% to 100%, the sensitivity of ketones, alcohols and aromatics was reduced by 30.9-73.0%, 40.3-64.3% and 75.1-91.6%, respectively. However, increasing humidity significantly enhanced the resolution of ketones and alcohols in the ranges of 1.82-11.82 times and 1.23-6.69 times, respectively, and hardly affected that of aromatics. Consequently, the appropriate humidity of carrier gas is of great importance in the use of UV-FAIMS.