Materials and methods of synthesizing mixed-layered bismuth oxy-iodine materials, which can be synthesized in the presence of aqueous radioactive iodine species found in caustic solutions (e.g. NaOH or KOH). This technology provides a one-step process for both iodine sequestration and storage from nuclear fuel cycles. It results in materials that will be durable for repository conditions much like those found in Waste Isolation Pilot Plant (WIPP) and estimated for Yucca Mountain (YMP). By controlled reactant concentrations, optimized compositions of these mixed-layered bismuth oxy-iodine inorganic materials are produced that have both a high iodine weight percentage and a low solubility in groundwater environments.