The thermodynamic and X-ray reflectivity studies were applied to the adsorbed films of 1-eicosanol, partially hydrogenated perfluorodecanol, and their mixtures at the hexane/water interface and clearly demonstrated the existence of domains. The thermodynamic and FTIR studies on ethyleneglycol monododecyl ether system and the thermodynamic and total reflection XAFS studies on dodecyltrimethylammonium bromide system at air/water interfaces confirmed that the inhomogeneous structure is rather generally observed in the adsorbed films. The knowledge from the thermodynamic and structure studies has been combined and further utilized in the mesoscopic thermodynamic formulation on the Gibbs films at soft interfaces.