The electronic structure and the Li diffusion paths in the lithium doped lanthanum titanate have been studied. The band dispersion and the density of states (DOS) are calculated using the linear-muffin-tin-orbital (LMTO) method. The model structure used contains La-rich and La deficient layers, with the 2a(p) x 2a(p) x 2a(p) unit cell and base centered C symmetry. The primitive cell contains 20 atoms represented by La3LiTi4O12. The energy contour map, where Li ions are assumed to move within the La-deficient (002) layer, shows that the stable position of Li ions is off centers of the vacant La sites and that Li ions migrate through the bottlenecks at 2c sites surrounded by four oxygen ions. (c) 2006 Elsevier B.V. All rights reserved.