The adsorption excess isotherms of ethanol–water and propanol–water mixtures are studied on a series of carbon molecular sieves with well-separated micro- and mesoporosity at 298.15 K. The preferential adsorption of one component from a mixture is measured by using vibration densitometry for the concentration analysis. Microcalorimetrically measured enthalpies, which are released upon immersion of the carbon materials in the binary mixtures, complement the adsorption excess data. It is shown that (i) density measurements are well applicable for studying liquid-phase adsorption, (ii) liquid-adsorption isotherms are sensitive to smallest chain length differences of the adsorptives, (iii) the calculated separation diagrams depend strongly on the assumptions about the adsorbed phase, and (iv) the combined determination of gas, vapor and liquid adsorption isotherms and immersion enthalpies offers advantages for the analysis of complex adsorption systems.