Polystyrene/divinylbenzene (PS-DVB) macroporous monoliths obtained using highly concentrated emulsions as templates show a superhydrophobic behaviour, restricting their potential technological applications, especially those related to adhesion and wetting. Air plasma treatments were carried out in order to modulate wetting properties, modifying the surface chemical composition of macroporous polystyrene/divinylbenzene materials. The superhydrophobic behaviour was rapidly suppressed by air plasma treatment, greatly reducing the water contact angle, from approximately 150 degrees to approximately 90 degrees, in only 10 seconds of treatment. The new surface chemical groups, promoted by plasma active species, were characterized by surface analysis techniques with different depth penetration specificity (contact angle, XPS, FTIR and SEM). Results demonstrated that very short treatment times produced different chemical functionalities, mainly C-O, C=O, O-C=O and C-N, which provide the materials with predominantly acidic surface properties. However, plasma active species did not penetrate deeply through the interconnected pores of the material. FTIR analysis evidenced that the new hydrophilic surface groups promoted by plasma active species are in a negligibly concentration compared to bulk chemical groups, and are located in a very thin surface region on the PS-DVB monolith surface (significantly below 2 microm). XPS analysis of treated monoliths revealed a progressive increase of oxygen and nitrogen content as a function of plasma treatment time. However, oxidation of the PS-DVB monoliths surface prevails over the incorporation of nitrogen atoms. Finally, SEM studies indicated that the morphology of the plasma treated PS-DVB does not significantly change even for the longest air plasma treatment time studied (120 s).