The photoluminescence properties of silver species, including Ag + , Ag + -Ag + , Ag 0 , and Ag nanoparticles in various matrices, such as gel and glass have been extensively reported. In the present study, we present the preparation of silver including SiO 2 three-dimensionally ordered macroporous (3DOM) materials and investigate the existing states and photoluminescence property of silver in the SiO 2 3DOM materials. The results show that only Ag + ions exist in the SiO 2 3DOM materials sintered at temperature below 400 C. With the increasing sintering temperature, the Ag + ions gradually transform into Ag + -Ag + , where simultaneously, a part of Ag + -Ag + transform into Ag nanoparticles. The Ag + -Ag + and Ag nanoparticles are formed in the SiO 2 3DOM materials sintered at temperature from 450 to 650 C. Finally, only Ag nanoparticles occur in the SiO 2 3DOM materials prepared at 750 C. The formation mechanisms of Ag species were discussed in the SiO 2 3DOM materials.