CdIn2O4 hollow spheres were synthesized by a self-template method. Cadmium nitrate (Cd(NO3)(2)center dot 4H(2)O) and indium nitrate (In(NO3)(3)center dot 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 CdIn2O4 hollow spheres was proposed, And pure phase of CdIn2O4 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.