Controlling the transport of lithium (Li) ions and their reaction with electrodes is central in the design of Li-ion batteries for achieving high capacity, high rate, and long lifetime. The flexibility in composition and structure enabled by tailoring electrodes at the nanoscale could drastically change the ionic transport and help meet new levels of Li-ion battery performance. Here, we demonstrate that radial heterostructuring can completely suppress the commonly observed surface insertion of Li ions in all reported nanoscale systems to date and to exclusively induce axial lithiation along the [111] direction in a layer-by-layer fashion. The new lithiation behavior is achieved through the deposition of a conformal, epitaxial, and ultrathin silicon (Si) shell on germanium (Ge) nanowires, which creates an effective chemical potential barrier for Li ion diffusion through and reaction at the nanowire surface, allowing only axial lithiation and volume expansion. These results demonstrate for the first time that interface and bandgap engineering of electrochemical reactions can be utilized to control the nanoscale ionic transport/insertion paths and thus may be a new tool to define the electrochemical reactions in Li-ion batteries.