A nano-Si/TiO2 core–shell nanostructured electrode was synthesized using sol–gel method. The TiO2 shells were made with 10-nm thickness, and were structurally stable upon the intercalation/deintercalation of Li+, improve the cyclability of the Si electrode during cycling. The nano-Si/TiO2 core–shell nanostructured electrode showed a reversible capacity of ca. 1250mA hg−1 over 50 cycles. The reaction mechanism between the nano-Si/TiO2 core–shell nanostructured electrode and Li was investigated by ex situ analyses.