High silica glass is a potential luminescence material in the future, whose photoluminescence properties are seriously influenced by phase separation temperature in the procedure. Porous glass with different phase separation temperatures and Eu2+/Dy3+ co-doped high silica luminescence glass with the same adsorption conditions are prepared. The specific surface area parameters of porous glass and the emission spectra of corresponding high silica luminescence glass are measured. The specific surface area measurement results indicate that the specific surface area of porous glass decrease firstly and then increase when the phase separation temperature is rising. The emission spectra of high silica luminescence glass indicate that the positions of characteristic peaks of high silica luminescence glass remain unchanged, while the emission intensity decreases firstly and then increases when the phase separation temperature is rising. Porous glass with phase separation temperature 620 ℃ has relative maximal specific surface area and corresponding high silica luminescence glass has the maximal emission intensity.