AbstractMacroporous polystyrene/divinylbenzene (PS‐DVB) monoliths were obtained using highly concentrated W/O emulsions as templates. These monoliths are of interest due to the high potential applications for catalysis, scaffolds for tissue engineering, filters, membranes, or drug delivery systems. Dynamic wetting behavior through the polymer monolith is directly related to contact angle. For this reason, in this paper we investigate the relationship between contact angle, morphology, and chemical composition of the dense skin layer and the highly porous interior surface of PS‐DVB porous monoliths.Whereas the dense skin layer exhibits a Wenzel regime using water as wetting liquid, the highly porous interior surface exhibits a Cassie–Baxter regime. This behavior is correlated with the roughness observed by scanning electron microscopy (SEM). However, the observed contact angle hysteresis seems to indicate that factors other than surface roughness should be taken into account. For this reason, chemical composition was also studied by elemental microanalysis and X‐ray photoelectron spectroscopy (XPS). The differences in chemical composition observed between the dense skin layer and the highly porous interior surface, according to the wetting model for a heterogeneous surface proposed by Johnson and Dettre, seems also to contribute to the wetting hysteresis. The different wetting between the dense skin layer and the highly porous interior surface results in a dual wettability phenomenon, in which a liquid wets the dense skin layer and does not penetrate into the highly porous interior of the PS‐DVB monoliths. This phenomenon can be of relevance in absorption or desorption processes such as in drug delivery processes. Copyright © 2009 John Wiley & Sons, Ltd.