Atmospheric air, being also a moist gas, is present as a working medium in various areas of technology, including the areas of airframe aerodynamics and turbomachinery. Issues related to the condensation of water vapor contained in atmospheric air have been intensively studied analytically, experimentally and numerically since the 1950s. An effort is made in this paper to present new, unique and complementary results of the experimental testing of moist air expansion in the de Laval nozzle. The results of the measurements, apart from the static pressure distribution on the nozzle wall and the images obtained using the Schlieren technique, additionally contain information regarding the quantity and quality of the condensate formed due to spontaneous condensation at the transition from the subsonic to the supersonic flow in the nozzle. The liquid phase was identified using the light extinction method (LEM). The experiments were performed for three geometries of convergent–divergent nozzles with different expansion rates of 3000, 2500 and 2000 s−1. It is shown that as the expansion rate increases, the phenomenon of water vapor spontaneous condensation appears closer to the critical cross-section of the nozzle. A study was performed of the impact of the air relative humidity and pollution on the process of condensation of the water vapor contained in the air. As indicated by the results, both these parameters have a significant effect on the flow field and the pressure distribution in the nozzle. The results of the experimental analyses show that in the case of the atmospheric air flow, in addition to the pressure, temperature and velocity, other parameters must also be taken into account as boundary parameters for possible numerical analyses. Omitting information about the air humidity and pollution can lead to incorrect results in numerical simulations of transonic flows of atmospheric air. The presented results of the measurements of the moist air transonic flow field are original and fill the research gap in the field of experimental studies on the phenomenon of water vapor spontaneous condensation.