In the present work, Eu2+/Dy3+ co-doped high silica glasses with different process parameters were prepared and the effect of critical process parameters including phase separation temperature, solution concentration and sintering temperature on the luminescence properties of Eu2+/Dy3+ co-doped high silica glasses was investigated by means of measuring pore surface parameters of porous glasses, emission spectra, infrared absorption spectra and densities of high silica glasses. Pore structure parameters of porous glass samples and emission spectra of corresponding high silica glass samples with different phase separation temperatures show that the phase separation temperature has indirect effect on luminescence properties of high silica glass by influencing specific surface area value of corresponding porous glass. Specific surface area of porous glass changes when phase separation temperature changes. High silica glass achieves maximum emission intensity when the maximum specific surface area of porous glass is obtained. Luminescence intensity of high silica glass increases when specific surface area of porous glass increases. Emission spectra of high silica glass samples with different solution concentrations show that the emission intensities of Eu2+ and Dy3+ in high silica glass are enhanced with the increase in the Dy3+ concentration in solution; when the Dy3+ concentration is beyond 0.1 mol·L-1, the emission intensities of Eu2+ and Dy3+ in high silica glass are both decreased due to the occurring of concentration quench of Dy3+ in the glass. Emission spectra and infrared absorption spectra of high silica glass samples with different sintering temperatures show that the emission intensity of high silica glass is increased with the increase in the sintering temperature because the content of residual hydroxyl groups —OH in the glass is decreased; when the sintering temperature is beyond 1 000 ℃, the high silica glass exhibits crystalline and the luminescence intensity decreases.