Carbon nanotube (CNT) and TiO2 nanofibre composite films are prepared and used as anode materials for lithium ion batteries (LIBs) without the use of binders and conventional copper current collector. The preliminary experimental results from X-ray diffraction, scanning electron microscopy and transmission electron microscopy suggest that the TiO2 nanofibres were well-dispersed and interwoven by the CNTs, forming freestanding, bendable and light weighted composite. In comparison with TiO2 nanofibre based LIBs, the CNTs could significantly improve the battery performance due to their high conductivity property and 3D network morphology. In both 1–3V and 0.01–3V testing voltage ranges, the as-prepared composites show excellent reversible capacity and capacity retention. The superior lithium storage capacity of the CNT/TiO2 composite was mainly attributed to dual functions of the CNTs – the CNTs not only provide conductive networks to assist the electron transfer but also facilitate lithium ion diffusion between the electrolyte and the TiO2 active materials by preventing agglomeration of TiO2 nanofibres. This work demonstrates that the CNT–TiO2 composite film could be one type of potential electrode material for large-scale LIB applications.