Na3[Ti2P2O10F] was synthesized by a hydrothermal method. It has an open framework structure consisting of TiFO5 octahedra and PO4 tetrahedra. The feasibility of Na3[Ti2P2O10F] as an anode material for lithium-ion batteries was first studied. Na3[Ti2P2O10F] exhibits a reversible capacity of more than 200 mAh g–1 at a discharge/charge current rate of 20 mA g–1 (∼0.1 C) and 105 mA g–1 at a discharge/charge current rate of 400 mA g–1 (∼2 C) with a lower intercalation voltage. The result of in situ X-ray diffraction test shows the structural evolution during the first discharge/charge cycle. The structure of Na3[Ti2P2O10F] was kept during discharge/charge with a slight change of the lattice parameters, which indicates a lithium solid solution behavior.