This paper describes a modified colloidal crystal templating method to prepare three-dimensionally ordered macroporous (3DOM) β-Bi2O3. The 3DOM β-Bi2O3 materials exhibit higher specific capacities and better capacity retention than conventional β-Bi2O3 nanoparticles as anode materials for Li-ion batteries. The initial discharge capacity of 3DOM β-Bi2O3 was as high as 1296mAhg−1 and the fourth discharge capacity was 526mAhg−1, whereas the discharge capacity of conventional non-templated β-Bi2O3 was only 299mAhg−1 after 4 cycles at a current rate of 0.2C. The improved electrochemical behavior of the 3DOM β-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 β-Bi2O3.