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CdS nanocrystalline were prepared by precipitation from a mixture of aqueous solutions of cadmium salts and sulfur salts without adding any surface-termination agent. Their crystal structures and particle sizes were determined by X-ray diffraction (XRD). The CdS nanocrystalline precipitated from different precursors exhibited three cases: cubic phase  hexagonal phase and a mixture of cubic and hexagonal phases. The photoluminescence (PL) of cadmium salt precursors and CdS nanocrystalline is also analyzed. Similar spectral band structure of cadmium salt precursors and CdS nanocrystalline is found. The spectral intensity of the CdS-Cd rich and CdS-S rich nanocrystalline shows that the precursors themselves have important effect on the PL of CdS nanocrystalline.