The goal of our research is to use anionic templating in order to develop new extended cationic structures of various dimensionalities. Such materials have potential applications in a host of anion-based applications, including ion exchange, pollutant trapping and base catalysis. These cationic structures are made by solvothermal synthesis, using thermally stable but weakly coordinating anions as templates to direct the formation of a positively charged host. Our focus has been on lower group 14 and 15 elements as metal centers for the synthesis of these inorganic materials. Due to the versatility of coordination numbers and possible ligand types, the Pb- and Bi-systems have yielded particularly interesting cationic structures. Selected transition metals have also been investigated. In addition to details regarding the synthesis and characterization of these materials, the physicochemical properties will also be discussed. In particular, we will present ion exchange results for a variety of inorganic and organic anions.