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. 1250 mA h g(-1) over 50 cycles. The reaction mechanism between the nano-Si/TiO2 core-shell nanostructured electrode and Li was investigated by ex situ analyses. (C) 2013 Elsevier B.V. All rights reserved.