In this paper, we report on fast permeation rate and reaction of hydrogen gas in alumino-silicate glasses to provide new functional properties. Eu3+:Al2O3-SiO2 glass was prepared with high europium concentration and heat treated in hydrogen gas atmosphere. The approach involves the determination of diffusion coefficients by measuring both hydrogen gas permeation and the hydroxyl formation in addition to the reduction of Eu3+ into Eu2+. The diffusion coefficients, determined from the gas permeation experiment, were two orders of magnitude higher than those calculated from the formation of hydroxyl bonds. The high diffusion coefficient was discussed relating with the gas solubility and the number of reduction sites. It was also found that the present glass exhibits a permeation rate of hydrogen gas higher than that of SiO2 glass by 103 times.