The uptake of strontium ions from an aqueous solution by fibrous cerium(IV) bis(monohydrogenphosphate) has been studied from the viewpoints of the immobilization of strontium in radioactive waste by a batchwise operation in the temperature range from 25 to 250 °C. Strontium ions can be exchanged below 100 °C following an ion-exchange reaction between hydrogen ions of the phosphate groups. In contrast, strontium ions can be effectively immobilized under hydrothermal conditions accompanied by a structural change of the exchanger, where divalent strontium ions are incorporated into the monazite-like compound to compensate tetravalent cerium ions in trivalent cerium orthophosphate system. This phenomenon is peculiar to alkaline earth metal ions, since the monazite-like compounds were obtained in the presence of Ca2+ and Ba2+, while this phenomenon was absent in the presence of Cu2+ or Ni2+.