CdIn(2)O(4) hollow spheres were synthesized by a self-template method. Cadmium nitrate (Cd(NO(3))(2).4H(2)O) and indium nitrate (In(NO(3))(3).4.5H(2)O) were used as raw materials. XRD and SEM were employed to characterize the structures and morphologies of as-grown samples. The effects of Cd/In ratios on the compositions, morphologies, and photocatalytic activities have been systematically investigated. A self-template growth mechanism of CdIn(2)O(4) hollow spheres was proposed. And pure phase of CdIn(2)O(4) can be obtained with Cd/In ratio of 1.3:2 annealing at 800 degrees C according to our experiments. The sample with the Cd/In ratio of 1.4:2 exhibited the highest photocatalytic efficiency, and more than 80% of Methylene Blue molecules can be decomposed in 180 min.