The statistical properties of atmospheric water vapor mixing ratio (WVMR) determined as the ratio of Raman lidar signals backscattered from water vapor and nitrogen molecules are studied. It is shown that WVMR estimates can be biased by a small percentage at low signal photon-counting rates due to fluctuations in the nitrogen signal in the denominator of the ratio, the magnitude of the bias being linked to the signal-to-noise ratio of the nitrogen signal. This is particularly important when unbiased estimates are required as in the case of climate studies and global positioning system (GPS) signal calibration. Different bias corrections and a modified ratio formulation are proposed in order to correct or eliminate this bias. The method is successfully applied in processing signals obtained with an experimental Raman lidar system devoted to calibrate GPS signals for slant path delays. It is shown to reduce biases into negligible values in both WVMR and wet path delay estimates in the range interval of 0-7 km.