In order to evaluate the possibility of three-dimensional (3D) architecture of rechargeable lithium ion batteries, three dimensionally ordered macroporous (3DOM) TiO2 film electrodes have been prepared by a colloidal crystal templating approach. X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and the discharge and charge measurements were used to characterize their structures and electrochemical properties. These results indicated the highly ordered 3D macroporosity and the inorganic framework of anatase TiO2 at calcination temperatures of 500 degrees C were achieved. After Li ion insertion, the destruction of 3DOM TiO2 film was found, and it should be responsible for the capacity fade of the Li/3DOM TiO2 cell. (c) 2006 The Electrochemical Society.