Our research involves the development of new cationic materials for anion-based applications. We report the solvothermal synthesis and characterization of Pb3F5NO3, a new layered lead fluoride material that, unlike the majority of layered and open-framework materials, is cationic in charge. The structure consists of polyhedral lead centers connected by doubly and triply bridging fluoride groups. We quantitatively exchanged the interlamellar nitrate groups of Pb3F5NO3 for dichromate, under ambient aqueous conditions. Nuclear magnetic resonance and UV-vis spectroscopy show the reaction proceeds to 61.0% completion in several days. The material is also stable to 450 degreesC, which is vastly superior to organic resins that are still the standard for anion-exchange. The presence of extraframework anions also opens up other potentially unique anion-based properties, such as new catalytic reactions, anion intercalation, or growth of anionic clusters within the void spaces of the cationic material.