Hollow zinc oxide microcapsules have been synthesized by a sacrificial template route involving the chemical bath deposition of nanostructured zinc oxide thin films on sulfonate-modified polystyrene microspheres and subsequent removal of the polymer core by dissolution in a solvent or by thermolysis. Scanning electron micrographs show that uniform coating of the templates is achieved when ZnO is deposited from a solution containing zinc acetate, the polymer polyvinylpyrrolidone, and a base in methanol, and that the ZnO shells remain intact after removal of the cores. A focused ion beam is used to cut slices from the spheres and demonstrate their inner morphology and hollowness. X-ray diffraction yields evidence that the shells consist of nanocrystalline ZnO with the zincite structure.