A facile method with interface assembly was developed to prepare TiO2/CdS composite hollow microspheres. By changing reactant concentration, stirring rate, and temperature, the hollow microspheres could be controlled in diameter, shell thickness, and composition. The morphology, structure, composition, and photoluminescence (PL) property of the hollow spheres were investigated with SEM, TEM, X-ray diffraction, and spectroscopic techniques. In photoluminescence (PL) spectra, a strong PL band appeared in the bluish violet wavelength range.