In contrast to classical surfactants, the knowledge about the self-organization of alkanes and their hydrophobic derivatives is still limited. In this paper, we present the results of the studies of self-assembly of long-chain dialkylthioethers at the air/water interface. The substitution of one methylene group by the thioether divalent sulfur introduces significant dipole moment to the alkane chain without affecting the hydrophobicity, which profoundly influences the self-assembly of these molecules. Depending on the location of the thioether group in the hydrophobic chain, the investigated molecules can form Langmuir monolayers, which are stabilized by the thioether-water H-bonds formation, or random multilayers. The structures of the monolayers were investigated with the application of Grazing Incidence X-ray Diffraction. To elucidate important structural differences between thioether and alkane monolalyers of the same hydrocarbon chain length, we applied the methods of quantum chemistry (ETS-NOCV calculations). It turned out that the introduction of one sulfur atom affects the distribution of electron density not only in the proximity of this atom but generally along the chain. The combination of experimental and calculation methods provides to the better understanding of the fundamental question of the self-organization of long-chain alkanes and their non-amphiphilic derivatives at interfaces. (C) 2013 Elsevier Inc. All rights reserved.