The arrangement of liquid molecules on surfaces bristling with alkyl chains is deduced from adsorption studies, X-ray powder diffraction data, and microcalorimetric measurements of swelling-type layered materials, especially clay minerals. Small polar molecules such as water, ethanol, formamide, dimethylsulfoxide, and aromatic compounds are clustered between the alkyl chains pointing away from the surface. The energetic contribution related to the movement of the alkyl chains from direct contact with the surface atoms into upright positions is decisive. The importance of the interactions between the liquid molecules on the structure of the adsorption layer is clearly indicated by the changes of the adsorption layer thickness by salt addition. Thermodynamic data are obtained from surface excess adsorption isotherms from binary liquid mixtures combined with microcalorimetric measurements. Long-chain adsorptives such as long-chain alcohols interact with the surface alkyl chains by forming stable bimolecular films. These films undergo a series of higher-order phase transitions into kink- and gauche-block structures as the consequence of rotational isomerization of the alkyl chains. Such transitions are considered elementary processes in self-assembling films (layer-by-layer deposition, fuzzy films, Langmuir-Blodgett technique), and lipid membranes.