Coaxial carbon/metal oxide/aligned carbon nanotube (ACNT) arrays over stainless-steel foil are reported as high-performance binder-free anodes for lithium ion batteries. The coaxial arrays were prepared by growth of ACNTs over stainless-steel foil followed by coating with metal oxide and carbon. The carbon/manganese oxide/ACNT arrays can deliver an initial capacity of 738 mAh g−1 with 99.9 % capacity retention up to 100 cycles and a capacity of 374 mAh g−1 at a high current density of 6000 mA g−1. The external carbon layer was recognized as a key component for high performance, and the mechanism of performance enhancement was investigated by electrochemical impedance spectroscopy, electron microscopy, and X-ray diffraction analysis. The layer increases rate capability by enhancing electrical conductivity and maintaining a low mass-transfer resistance and also improves cyclic stability by avoiding aggregation of metal-oxide particles and stabilizing the solid electrolyte interface. The resultant principle of rational electrode design was applied to an iron oxide-based system, and similar improvements were found. These coaxial nanotube arrays present a promising strategy for the rational design of high-performance binder-free anodes for lithium ion batteries.