Highly efficient visible-light-active CuO/Cu2O heterostructured composite hollow microspheres were successfully developed under an appropriate molar ratio of the copper precusor to the reductant ― d-sorbitol for photocatalytic degradation of methyl orange with outstanding photostability. The hollow microsphere structure composite displayed high visible-light photocatalytic activity and reproducibility toward the degradation of methyl orange, due to its high adsorption capacity, enhanced light scattering effects, high throughput hollow reaction regions within the hollow structures and decreased recombination of photogenerated electrons and holes. This demonstrated useful hollow microspheres act as an example of developing highly efficient heterostructured binary metal oxides for photocatalytic water purification.