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Rare earth phosphate core/shell nanostructures were synthesized via facile ultrasound irradiation method. XRD and TEM were em-ployed to characterize the structure and morphology properties. The photoluminescence (PL) properties of TbPO4/CePO4 and CePO4/TbPO4 core/shell nanorods were studied to explore the energy transfers from Ce3+ to Tb3+. In the Ce0.9Tb0.1PO4/LaPO4 core/shell nanorods, the PL intensity of Ce0.9Tb0.1PO4 nanorods was enhanced when the LaPO4 shells were coated.