Integrated water vapor (IWV) is a crucial parameter for tropospheric sounding and weather prediction applications. IWV is essentially calculated using observations from global navigation satellite systems (GNSS). Presently, the Galileo satellite system is further developed, including more visible satellites that transmit multi-frequency signals. This study aims to evaluate the accuracy of real-time IWV estimated from a triple-frequency Galileo-only precise point positioning (PPP) processing model utilizing E1, E5a, E5b, and E5 observations, which is not addressed by the previous studies. For this purpose, Galileo datasets from 10 global reference stations spanning various 4-week periods in the winter, spring, summer, and fall seasons are acquired. To process the acquired datasets, dual- and triple-frequency ionosphere-free PPP solutions are used, including E1E5a PPP, E1E5aE5b PPP, and E1E5E5b PPP solutions. The publicly available real-time products from the Centre National d’Etudes Spatiales (CNES) are utilized. The real-time IWV values are computed and then validated with the European Centre for Medium-Range Weather Forecasting (ECMWF) reanalysis products (ERA5) counterparts. The findings demonstrate that the root mean square error (RMSE) of the estimated IWV is less than 3.15 kg/m2 with respect to the ECMWF ERA5 counterparts. Furthermore, the E1E5aE5b PPP and E1E5E5b PPP models enhance the IWV’s accuracy by about 11% and 16%, respectively, compared with the E1E5a PPP model.