The unique TiO2–C/MnO2 core–double-shell nanowires are synthesized for the first time using as anode materials for lithium ion batteries (LIBs). They combine both advantages from TiO2 such as excellent cycle stability and MnO2 with high capacity (1230 mA h g–1). The additional C interlayer intends to improve the electrical conductivity. The self-supported nanowire arrays grown directly on current-collecting substrates greatly simplify the fabrication processing of electrodes without applying binder and conductive additives. Each nanowire is anchored to the current collector, leading to fast charge transfer. The unique one-dimensional core–double-shell nanowires exhibit enhanced electrochemical performance with a higher discharge/charge capacity, superior rate capability, and longer cycling lifetime.