Novel chemically bonded phosphate ceramics have been investigated for the capture and stabilization of volatile fission‐product radionuclides. We have used low‐temperature processing to fabricate zirconium phosphate and zirconium/magnesium phosphate composites. A zirconium/magnesium phosphate composite has been developed and shown to stabilize ash waste that has been contaminated with a radioactive surrogate of the 137Cs and 90Sr species. Excellent retention of cesium in the phosphate matrix system was observed in both short‐ and long‐term leaching tests. The retention factor determined by the USEPA Toxicity Characteristic Leaching Procedure was one order of magnitude better for cesium than for strontium. The effective diffusivity, at room temperature, for cesium and strontium in the waste forms was estimated to be as low as 2.4 × 10−13 and 1.2 ×10−11 cm2/s, respectively. This behavior was attributed to the capture of cesium in the layered zirconium phosphate structure via an intercalation ion‐exchange reaction, followed by microencapsulation. However, strontium is believed to be precipitated out in its phosphate form and subsequently microencapsulated in the phosphate ceramic. The performance of these final waste forms, as indicated by the compression strength and the durability in aqueous environments, satisfies the regulatory criteria.