Abstract The aim of this paper is to propose a method to determine the chemical potential of two miscible components of a solution in porous media, particularly in the case of an unsaturated soil. It is limited to the capillary state; the equilibrium of the liquid phase in the soil is determined by gas–liquid interfaces whose geometry obeys Laplace’s law. Deduction of the chemical potential of the two components from the chemical potential of pure water is based on the assumption that, for the same volume occupied by the fluid phase in the porous medium, the geometry of the fluid phase is independent of the composition of the solution. The expressions of the chemical potentials of the two components were established. They show the superposition of two effects: the effect of interfacial forces and the effect of the presence of the other component. A study of the water–alcohol solution in a clayey silty sand soil was then conducted to alcohol mole fractions between 0 and 0.15 and water content in the 5%–15% range. In this field, the chemical potential of the water was seen to be affected by the capillary effects below a water content of 10%. Above that, its variation as a function of the mole fraction of alcohol differed little from that of the potential of the water in a free solution. The chemical potential of the alcohol was little affected by the capillary effects.