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Nano-sized GdPO4:Eu3+ hierarchical hollow spheres were successfully synthesised through chemical conversion using Gd(OH)CO3:Eu3+ nanospheres as templates. The obtained hollow spheres were composed of primary nanowires. Based on the time-dependent experiments, the hollow shells were proposed to be formed through chemical conversion from the precursor spheres. The as-prepared GdPO4:Eu3+ hollow spheres exhibit good photoluminescence performance. Furthermore, the current method can serve as a general way for the synthesis of rare-earth phosphates hollow spheres.