A novel measurement concept specifically tuned to monitoring tropospheric water vapour’s vertical distribution has been demonstrated on a theoretical basis and is currently under development for space deployment. The NDSA (Normalised Differential Spectral Attenuation) technique derives the integrated water vapour (IWV) along the radio link between a transmitter and a receiver carried by two LEO satellites, using the linear correlation between the IWV and a parameter called spectral sensitivity. This is the normalised incremental ratio of the spectral attenuation at two frequencies in the Ku and K bands, with the slope of the water vapour absorption line at 22.235 GHz. Vertical profiles of WV can be retrieved by inverting a set of IWV measurements acquired in limb geometry at different tangent altitudes. This paper provides a comprehensive insight into the NDSA approach for sounding lower tropospheric WV, from the theoretical investigations in previous ESA studies, to the first experimental developments and testing, and to the latest advancements achieved with the SATCROSS project of the Italian Space Agency. The focus is on the new results from SATCROSS activities; primarily, on the upgrading of the instrument prototype, with improved performance in terms of its power stability and the time resolution of the measurements. Special emphasis is also placed on discussing tomographic inversion methods capable of retrieving tropospheric WV content from IWV measurements, i.e., the least squares and the external reconstruction approaches, showing results with different spatial features when applied to a given atmospheric scenario. The ultimate goal of deploying the NDSA measurement technique from space is thoroughly examined and conclusions are drawn after presenting the results of an Observing System Simulation Experiment conducted to assess the impact of NDSA data assimilation on environmental model simulations.