The structure and electrochemical performance of sodiated iron phosphate were investigated by means of X-ray diffraction, high-resolution transmission electron microscopy and electrochemical measurements. The results indicate that after the sodiation process, all FePO4 samples transform into the amorphous sodium iron phosphate and crystallite NaFePO4, namely triphylite NaFePO4 for amorphous FePO4 and maricite NaFePO4 for trigonal FePO4, respectively. The amorphous FePO4 samples show excellent electrochemical performance in terms of cyclic stability and discharge capacity, while trigonal FePO4 displays poor electrochemical performance. The outstanding electrochemical performance of amorphous FePO4 was attributed to the amorphous and triphylite NaFePO4 with high electrochemical activity. Those findings indicate that amorphous FePO4 can be transformed into active NaFePO4, which may have great potential as an electrode material for sodium-ion batteries.