Microporous polymeric membranes are of interest for a variety of applications from advanced optical devices to novel templates for cell growth. Microporous materials are typically fabricated in a three-step process of template formation, matrix infusion, and template disintegration, where the template can be formed using lithographic or self-assembly methods. In this talk we present a novel, one-step method for producing uniform, ordered arrays of micro-scale holes and capturing those arrays within a mechanically stable PDMS elastomer film. The process occurs via evaporation of water from a reservoir and subsequent condensation of the vapor onto the uncured elastomer film. Unlike the formation of breath figures, which also involves condensation of vapor onto a surface, this process involves the slow heating of a constant volume of vapor and water. The spherical cavities that result from this process are less than ten micrometers in radius, and they are observed to organize into hexagonal arrays over an area of up to ten square centimeters. We demonstrate a plausible mechanism by which water droplets condense and grow on a liquid surface, become encapsulated once a critical size is reached, and organize into hexagonal clusters and arrays. The dependence of the resulting size of the microcavities on system variables is discussed.