Titanium oxyhydroxy-fluoride, TiO0.9(OH)0.9F1.2 · 0.59H2O rods with a hexagonal tungsten bronze (HTB) structure, was synthesized via a facile one-step solvothermal method. The structure, morphology, and component of the products were characterized by X-ray powder diffraction (XRD), thermogravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), ion chromatograph, energy-dispersive X-ray (EDX) analyses, and so on. Different rod morphologies which ranged from nanoscale to submicron scale were simply obtained by adjusting reaction conditions. With one-dimension channels for Li/Na intercalation/de-intercalation, the electrochemical performance of titanium oxyhydroxy-fluoride for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) was also studied. Electrochemical tests revealed that, for LIBs, titanium oxyhydroxy-fluoride exhibited a stabilized reversible capacity of 200 mAh gâ1 at 25 mA gâ1 up to 120 cycles in the electrode potential range of 3.0â1.2 V and 140 mAh gâ1 at 250 mA gâ1 up to 500 cycles, especially; for SIBs, a high capacity of 100 mAh gâ1 was maintained at 25 mA gâ1 after 115 cycles in the potential range of 2.9â0.5 V.