Organic films on deliquesced aerosols and cloud droplets lower the surface tension of water and may inhibit the exchange of water vapor and gases between the gas and the liquid phase, with important implications for aerosol and cloud microphysics and heterogeneous chemistry. This study provides an estimate of the solubility properties of surfactants in aerosol and fog/cloud water samples on the basis of the dilatational rheological properties of the surface films. The variations of surface tension induced by the fast expansion/compression of the films were measured by means of a drop shape tensiometer and were linked to the capacity of surfactants to exchange between the surface layer and bulk solution, and ultimately to their water-solubility. The results are in agreement with the properties of standards of soluble surfactants and can be interpreted by the theory of formation of hydrophilic adsorption layers. These findings suggest that the water-soluble organic compounds (WSOC) are the main contributors to the formation of films on cloud/fog droplets. It follows that the surface coverage of film-forming compounds is mainly controlled by the bulk concentration of WSOC, regardless of the available surface area. This also supports that the surface tension decreases observed under laboratory conditions actually occur in the atmosphere.