In this work, probabilistic aspects related to the heterogeneous nucleation on microporous hydrophobic surfaces, i.e. polymeric membranes, have been theoretically investigated to understand the ability of this innovative crystallization technique to promote the formation of different polymorphs. The theoretical results, which clarify the effects of physicochemical properties of membranes (i.e. porosity, contact angle between supersaturated solution, and polymeric substrate) on the nucleation process of polymorphs, have been used to discuss the experimentally observed selective crystallization of forms I and II of paracetamol. (C) 2008 Elsevier B.V. All rights reserved.