The electrochemical behavior of TiO2 anatase with a predominant (001) face (ANA001) was studied by cyclic voltammetry of Li insertion and chronoamperometry. Both voltammetric and chronoamperometric diffusion coefficients and rate constants proved the higher activity of ANA001 toward Li insertion compared to that of a reference anatase material (C240) with dominating (101) facets. The enhanced activity of the anatase (001) face for Li insertion stems from synergic contributions of a faster interfacial charge transfer at this surface and a facile Li transport within a more open structure of the anatase lattice in the direction parallel to the c-axis. Despite the larger particle size of ANA001, the values of integral charge capacity and Li-insertion coefficient further confirmed its improved Li-insertion properties. The results of this study further complete the analogous data published on single-crystal anatase electrodes and evidence their validity for nanocrystalline materials too. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3479192] All rights reserved.