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The optical properties of matrix of porous glasses and phase-separated glasses were investigated by visible spectroscopy and infrared spectroscopy. The experimental results show that, both the porous glasses and phase-separated glasses have very good light transmission in visible light region that wavelenth is longer than 560nm. The micropores of porous glasses and the boron-rich phase of phase-separated glasses have strong Rayleigh scatter effects on the visible light, the largest scatter occurrs at 360-370nm; the thicker the glasses, the larger the light scattering. Thus, the pore size distribution and the size of heterogeneous micro zone in boron-rich phase of phase-separated glasses can be measured. After coupled into porours glasses, the most intense absorption of hydrated ions of [Co(H2O)6]2+ shifts from 508nm to 515nm. The production of the most intense absorption and the red shift were owed to Jahn-Teller effect of octahedral field formed by six H2O molecular and perturbation effect resulted by microporous of porous glasses for its physics-chemical circumstance. As a result, the porous glasses are perfect optical function materials in visible region, which can be assembled by chemical method.