Nitrogen and fluorine co-doped Ti-oxide, TiO_1.9N_0.05F_0.15 (TiO₂(N,F)), with the anatase structure is prepared by the pyro-ammonolysis of TiF₃. For the first time it is shown that TiO₂(N,F) and anatase-TiO₂ are converted to nanosize-rutile structure by high energy ball milling (HEB). The polymorphs are characterised by X-ray diffraction, Rietveld refinement, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and Raman spectra. The Li storage and cycling properties are examined by galvanostatic cycling and cyclic voltammetry in the voltage range 1–2.8 V vs.Li at 30 mA g⁻¹. The performance of TiO₂(N,F) is much better than pure anatase-TiO₂ and showed a reversible capacity of 95 (±3) mA h g⁻¹ stable up to 25 cycles with a coulombic efficiency of ∼98%. Nano-phase rutile TiO₂(N,F) showed an initial reversible capacity of 210 mA h g⁻¹ which slowly degraded to 165 (±3) mA h g⁻¹ after 50 cycles and stabilised between the 50^th and 60^th cycle whereas the nano-phase rutile-TiO₂ (prepared by HEB of anatase-TiO₂) exhibited a reversible capacity of 130 (±3) mA h g⁻¹ which is stable in the range, 10–60 cycles. The crystal structure of anatase TiO₂(N,F) is not destroyed upon Li-cycling and is confirmed by ex situXRD and HR-TEM.