The estimation of the precipitable water vapour content (W) with high temporal and spatial resolution is of great interest to both meteorological and climatological studies. Several methodologies based on remote sensing techniques have been recently developed in order to obtain accurate and frequent measurements of this atmospheric parameter. Among them, the relative low cost and easy deployment of sun-sky radiometers, or sun photometers, operating in several international networks, allowed the development of automatic estimations of W from these instruments with high temporal resolution. However, the great problem of this methodology is the estimation of the sun-photometric calibration parameters. The objective of this paper is to validate a new methodology based on the hypothesis that the calibration parameters characterizing the atmospheric transmittance at 940nm are dependent on vertical profiles of temperature, air pressure and moisture typical of each measurement site. To obtain the calibration parameters some simultaneously seasonal measurements of W, from independent sources, taken over a large range of solar zenith angle and covering a wide range of W, are needed. In this work yearly GNSS/GPS datasets were used for obtaining a table of photometric calibration constants and the methodology was applied and validated in three European ESR-SKYNET network sites, characterized by different atmospheric and climatic conditions: Rome, Valencia and Aosta. Results were validated against the GNSS/GPS and AErosol RObotic NETwork (AERONET) W estimations. In both the validations the agreement was very high, with a percentage RMSD of about 6, 13 and 8% in the case of GPS intercomparison at Rome, Aosta and Valencia, respectively, and of 8% in the case of AERONET comparison in Valencia. Analysing the results by W classes, the present methodology was found to clearly improve W estimation at low W content when compared against AERONET in terms of %bias, bringing the agreement with the GPS (considered the reference one) from a %bias of 5.76 to 0.52.