The hydrophilic/hydrophobic behavior of two silica polymorphs (a finely ground cristobalite and a pyrogenic amorphous Aerosil) was studied by means of adsorption microcalorimetry, as a function of nature and extension of the surface hydroxylated layer. Water and two alcohols (methanol and tert-butyl alcohol) were used as probes for polar and apolar sites, available for H-bonding and for dispersion forces interactions. It was found that in most cases small portions of the surface were irreversibly modified upon the earliest contact with the probe, owing to dissociative reactions occurring at 303 K. However, the main process involved during the interaction was a reversible molecular adsorption : on both hydrophilic and hydrophobic SiO2 the process was by far more energetic for the two alcohols than for water, as indicated by the heat of adsorption values. The contribution of the dispersion forces to the overall energy of interaction on hydrophilic silica was approximate to 16 kJ/mol for methanol and approximate to 34 kJ/mol for tert-butyl alcohol. For hydrophobic silica the dispersive forces interaction was found to be a major component of the overall process, and the energetic described for hydrophilic silica was confirmed.