Single-crystalline TiOF2 nanocubes with edge length of around 200–300nm have been synthesized under hydrothermal conditions using titanium (IV) isopropoxide (TIP) as titanium source, HF as etchant. The corresponding hollow TiO2 nanocages with dominantly exposed {001} crystal planes can be easily obtained by calcinating TiOF2 nanocubes under air atmosphere. It is also found that the presence of acetic acid not only being chemical modifier of TIP to lower its reactivity at relatively acid environment, but also gives rise to a uniform hollow TiO2 nanocages which play the crucial role in hollow formation. The TiOF2 electrode presented here exhibits much excellent electrochemical performance. The initial high specific capacity of TiOF2 can be up to 1045mAhg−1 at a rate of 30mAg−1. The specific discharge capacity is 510mAhg−1 after 40 cycles.