Water vapor mixing ratio and relative humidity profiles were derived from the multi-wavelength Raman PollyXT lidar at the EARLINET site in Warsaw, using the Rayleigh molecular extinction calculation based on atmospheric temperature and pressure from three different sources: i) the standard atmosphere US 62, ii) the Global Data Assimilation System (GDAS) model output, and iii) the WMO 12374 radiosoundings launched at Legionowo. With each method, 136 midnight relative humidity profiles were obtained for lidar observations from July 2013 to August 2015. Comparisons of these profiles showed in favor of the latter method (iii), but it also indicated that the other two data sources could replace it, if necessary. Such use was demonstrated for an automated retrieval of water vapor mixing ratio from dusk until dawn on 19/20 March 2015; a case study related to an advection of biomass burning aerosol from forest fires over Ukraine. Additionally, an algorithm that applies thresholds to the radiosounding relative humidity profiles to estimate macro-physical cloud vertical structure was used for the first time on the Raman lidar relative humidity profiles. The results, based on a subset of 66 profiles, indicate that below 6 km cloud bases/tops can be successfully obtained in 53% and 76% cases from lidar and radiosounding profiles, respectively. Finally, a contribution of the lidar derived mean relative humidity to cloudy conditions within the range of 0.8 to 6.2 km, in comparison to clear-sky conditions, was estimated.