Observations of very low amounts of precipitable water vapor (PWV) by means of the Ground‐Based Millimeter wave Spectrometer (GBMS) are discussed. Low amounts of column water vapor (between 0.5 and 4 mm) are typical of high mountain sites and polar regions, especially during winter, and are difficult to measure accurately because of the lack of sensitivity of conventional instruments to such low PWV contents. The technique used involves the measurement of atmospheric opacity in the range between 230 and 280 GHz with a spectral resolution of 4 GHz, followed by the conversion to precipitable water vapor using a linear relationship. We present the intercomparison of this data set with simultaneous PWV observations obtained with Vaisala RS92k radiosondes, a Raman lidar, and an IR Fourier transform spectrometer. These sets of measurements were carried out during the primary field campaign of the Earth Cooling by Water vapor Radiation (ECOWAR) project which took place at Breuil‐Cervinia (45.9°N, 7.6°E, elevation 1990 m) and Plateau Rosa (45.9°N, 7.7°E, elevation 3490 m), Italy, from 3 to 16 March 2007. GBMS PWV measurements show a good agreement with the other three data sets exhibiting a mean difference between observations of ≃9%. The considerable number of data points available for the GBMS versus lidar PWV correlation allows an additional analysis which indicates negligible systematic differences between the two data sets.