Abstract The applications of calorimetric and ellipsometric methods to the understanding of adsorption phenomena occurring at the solid–liquid interface are presented with examples in the field of surfactant adsorption. The various experimental approaches are presented and compared, i.e., immersion calorimetry, titration calorimetry and liquid flow calorimetry. It is shown how they can be used to follow, in situ, the building steps of the surfactant adsorbed layer. On the other hand, ellipsometry allows the adsorption isotherm, the adsorption kinetics as well as the thickness of the adsorbed layer to be determined on well-defined flat surfaces. To cite this article: R. Denoyel, C. R. Geoscience 334 (2002) 689–702.