ZnO and ZnO–CuO composite hollow spheres were fabricated by using colloidal carbon spheres as templates. The morphology, structure and chemical composition of the as-prepared samples were investigated using field emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The photocatalytic activity of the hollow spherical products was evaluated by photocatalytic degradation of methylene blue (MB) aqueous solution at ambient temperature. The results indicated that the ZnO–CuO composite hollow spheres display higher photocatalytic efficiency than pure hollow ZnO products. The related photocatalytic mechanism was discussed based on the microstructure and properties of the ZnO and ZnO–CuO composite hollow spheres. The facile strategy for the preparation of ZnO–CuO hollow nanostructures can be applicable to the synthesis of other composite hollow spheres.