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Hierarchical hollow spherical CdS nanostructures were synthesized via simple microwave hydrothermal(M-H) process using CdCl2·H2O and Na2S2O3·5H2O as source materials and adding ethylenediaminetetraacetic acid (EDTA) as template.The obtained products were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM).Ultraviolet-Visible (UV-Vis) spectroscopy was used to study the optical properties of CdS.The results demonstrate that the hierarchical hollow spherical CdS with a diameter range of 400-600nm are self-assembled by 30nm nanoparticles and in a wurtzite structure.EDTA and microwave play an important role on the formation of the hollow hierarchical morphology.The effect of the microwave and possible growth mechanism were dicussed.Ultraviolet-Visible (UV-Vis) spectroscopy exhibits the CdS crystallites could be used as a potential blue light emitting material.