New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV)and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photolnminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS).