Advanced flexible electrode is crucial in the development of flexible energy storage devices for emerging wearable and portable electronics. Herein, a free-standing flexible mesoporous Li4Ti5O12-rGO (LTO-rGO) nanocomposite film is rationally designed and fabricated for lithium ion batteries (LIBs). This efficient synthesis involves the growth of lithium titanate hydrate (LTH) precursors on the graphene oxide (GO) by a hydrothermal reaction, assembly into LTH-GO film by vacuum filtration with some extra GO added, and subsequent conversion into LTO-rGO nanocomposite film through calcination. When rGO content in the LTO-rGO film is set, the addition sequence of GO is found to affect its textural and mechanical properties. The resultant free-standing LTO-rGO electrode, taking advantages of high Li4Ti5O12 loading of 73.9%, mesoporous layer-stacked channels with good electron/ion conductivity, good mechanical strength, and enlarged electrode/electrolyte contact area, delivers excellent electrochemical performance (e.g., specific capacity of 135.4 mAh g−1 at 40 C) over the electrode of conventional configuration. Moreover, no organic but all inorganic reagents are used in the synthesis, offering an eco-friendly, cost-efficient, and easily scalable way to fabricate binder-free flexible electrode for LIBs.