Transparent crystallized glass with a surface crystallization layer of sub-millimeter thickness was found in the glass compositions of 35BaO15TiO 2 50GeO 2 (BTG50), 28BaO18TiO 2 54SiO 2 (BTS54), and 35SrO20TiO 2 45SiO 2 (STS45), and the precipitated fresnoite-type crystalline phase showed nonlinear optical properties. XRD