LiFePO4 has shown considerable promise as a cathode material in Li-ion batteries due to its stability, low toxicity and high cyclability. However, the data on thermodynamic stability of olivine phase FePO4 (o-FePO4), the delithiated form of o-LiFePO4, remains scarce and contradictory. In this work, o-FePO4 was synthesized by chemical delithiation of o-LiFePO4 and characterized structurally and thermally. X-ray diffraction and absorption data indicate pure olivine phase, but with residual amount of Fe2+, most likely due to incomplete delithiation. Differential scanning calorimetry and thermal gravimetric analysis reveal that o-LixFePO4 decomposes exothermally above 550 °C with about 9% weight loss, the products being trigonal phase FePO4, Fe7(PO4)6, and LiPO3.