There is increasing interest in flexible, safe, high-power thin-film lithium-ion batteries which can be applied to various modern devices. Although TiO2 in rutile phase is highly attractive as an anode material of lithium-ion batteries for its high thermal stability and theoretical capacity of 336mAhg−1 and low price, its inflexibility and sluggish lithium intercalation kinetics of bulk phase strongly limit its practical application for particular in thin-film electrode. Here we show a simple way to prepare highly flexible self-standing thin-film electrodes composed of mesoporous rutile TiO2/C nanofibers with low carbon content (<15wt.%) by electrospinning technique with outstanding electrochemical performance, which can be applied directly as electrodes of lithium-ion batteries without the further use of any additive and binder. The atmosphere during calcination plays a critical role in determining the flexible nature of thin film and particle size of TiO2 in as-fabricated nanofibers. Big size (10cm×4cm), flexible thin film is obtained after heat treatment under 10%H2–Ar at 900°C for 3h. After optimization, the diameter of fibers can reach as small as ∼110nm, and the as-prepared rutile TiO2 films show high initial electrochemical activity with the first discharge capacity as high as 388mAhg−1. What is more, very stable reversible capacities of ∼122, 92, and 70mAhg−1 are achieved respectively at 1, 5 and 10C rates with negligible decay rate within 100 cycling times.