Nanocrystalline Ag doped silica inverse opals were prepared by a sol-gel chemistry method via templating of polystyrene colloidal crystals. The ordered structures of colloidal crystal templates and inverse opals are characterized by scanning electron microscopy. Ag nanocrystals size is estimated as 20~30nm by Scherrer Formula from X-ray diffraction. The color and the stop band of the inverse opals are characterized by transmission spectrum. And five emission peaks of the nanocrystalline silver clusters are observed from fluorescence spectrum.