We demonstrate an original and powerful concept for elaborating spontaneous, high fidelity patterns of nanoporosity from nanoscale building blocks using patterned surface chemistry (i.e., "surface energy gating") to corral the growth of colloidal structures at a solid surface. Composite films consisting of polymethylsilsesquioxane nanoparticles uniformly dispersed in polypropylene glycol polymer were examined at temperatures beyond the decomposition of the polymer as a function of the substrate surface energy to clarify nanoparticulate ensemble behavior. The principle behind this colloidal assembly can be understood by taking into consideration the entropy and enthalpy dictating the mutual interactions between substrate surface, polymeric solvent, and dispersed colloids in the decomposition regime. The relevance of this research is shown by demonstrating how the principle of surface energy gating can be utilized to achieve spontaneous and controllable spatial patterns of nanoporous, high surface area thin films in a cost-effective and energy-efficient manner via brief thermal exposure. The simplicity and general nature of this methodology are further exemplified by showing the facility with which high-contrast fluorescent bioconjugate arrays can be prepared from nanoporous organosilicate patterns. (C) 2011 Elsevier Inc. All rights reserved.