This paper describes a modified colloidal crystal templating method to prepare three-dimensionally ordered macroporous (3DOM) beta-Bi2O3. The 3DOM beta-Bi2O3 materials exhibit higher specific capacities and better capacity retention than conventional beta-Bi2O3 nanoparticles as anode materials for Li-ion batteries. The initial discharge capacity of 3DOMS-Bi2O3 was as high as 1296 mAhg(-1) and the fourth discharge capacity was 526 mA hg(-1), whereas the discharge capacity of conventional non-templated beta-Bi2O3 was only 299 mAhg(-1) after 4 cycles at a current rate of 0.2C. The improved electrochemical behavior of the 3DOM beta-Bi2O3 electrodes is attributed to the 3DOM architecture, which provides easy access for Li+ ions to the surface of active material nanoparticles and short diffusion paths within the macropore walls, and also to the unique tunnel structure of beta-Bi2O3. (C) 2016 Elsevier Ltd. All rights reserved.