To evaluate the potential of Raman lidar observations for measuring precipitable water vapor (PWV), PWV variations and distribution characteristics were investigated in Xi'an (34.233 • N, 108.911 • E), and its comparisons with meteorological parameters were also analysed. Comparisons of lidar PWV with radiosonde PWV verified the ability and accuracy of using Raman lidars for PWV measurements. The diurnal and monthly variation trends in PWV in different layers are first discussed via the statistical analysis of lidar data from November 2013 to July 2016; different proportions of PWV were found in different layers, and the PWV in each layer presented a slight diurnal change trend and consistent seasonal variation, which was relatively rich in summer, less so in spring and autumn, and relatively deficient in winter. Furthermore, correlation analyses between lidar PWV and meteorological parameters are explored. Water vapor pressure and surface temperature revealed the same inter-seasonal oscillation of PWV, with a correlation coefficient of~0.90. However, incomplete synchronization was found between PWV and relative humidity and precipitation parameters. Higher humidity appeared in the late summer and the beginning of autumn of each year, which was also the case for precipitation and precipitation efficiency. In addition, atmospheric water vapor density profiles and the obtained PWV by Raman lidar are discussed employing a rainfall case, and a comprehensive analysis with meteorological parameters is undertaken. The intensifying characteristics of vertical change in water vapor and the accumulation of PWV in the lower troposphere can be captured by lidar before the onset of rainfall. In contrast to the obvious diurnal change trend, such meteorological parameters as relative humidity, water vapor pressure, and dew-point temperature difference are accompanied with stable trends with a change rate of close to 0 in the rainfall processes; they also show high correlated variations with lidar PWV. Thus, with the advantage of lidar detection, investigation of water vapor profiles and PWV by Raman lidar, and the comprehensive correlation analyses with synchronic meteorological parameters can prove to be good indications of rainfall.