A metal film of Cu or Sn was vacuum-deposited on the surface of mesoporous anatase TiO2 electrodes, and the Li insertion/extraction behaviour was investigated by cyclic voltammetry and galvanostatic cycling. The morphological and structural characterization of metal-coated electrodes showed that the metallic layers do not alter the structure of anatase. The electrode surface modification made by thin-film deposition improves the kinetics of Li insertion/extraction and remarkably enhances the electrochemical performances in terms of capacity and stability, especially at high charge/discharge rates.