The electrochemical properties of lithium hexafluorometalates as positive electrode materials were studied. Trirutile-type Li<sub>2</sub>TiF<sub>6</sub> was synthesized through a complex-formation reaction under mild temperature conditions. In addition, a spray-drying technique was used to obtain electrodes with a large surface area. The electrochemical performance of the resultant Li<sub>2</sub>TiF<sub>6</sub> powders was investigated vs. Li metal as negative electrode. Li<sub>2</sub>TiF<sub>6</sub> exhibited an initial discharge capacity of 100 mAh g<sup>−1</sup> at 2.7 V.