The enthalpy of immersion for five activated carbons (with different surface chemistry) in cyclohexane and hexane was determined in order to observe the intensity of the solid–liquid interaction. The enthalpy of immersion was related to the properties of activated carbons, such as micropore volume, total basic groups content, and the EoWo product, that characterized each solid-liquid system. The values for the immersion enthalpy were between −21.2 and −91.7 J g−1 for cyclohexane and between −16.4 and −66.1 J g−1 for hexane. It showed greater interaction between the cyclohexane and the activated carbons and it was related to the properties of this adsorbate, such as molecular size and molecular arrangement. The difference in the enthalpy of immersion between the solvents per unit of micropore volume for the set of activated carbons was calculated obtaining a value of −487 J cm−3.