Boolean random sets are versatile tools to match morphological and topological properties of real structures of materials and particulate systems. Moreover, they can be combined in any number of ways to produce an even wider range of structures that cover a range of scales of microstructures through intersection and union. Based on well-established theory of Boolean random sets, this work provides scientists and engineers with simple and readily applicable results for matching combinations of Boolean random sets to observed microstructures. Once calibrated, such models yield straightforward three-dimensional simulation of materials, a powerful aid for investigating microstructure property relationships. Application of the proposed results to a real case situation yield convincing realisations of the observed microstructure in two and three dimensions. (C) 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.