We have demonstrated that 30BaO–15TiO2–30GeO2–25SiO2 (BTGS25) glass is a candidate for fiber-type nonlinear optical devices using crystallization of glass matrix. We determined the glass composition is suitable for crystallized fiber using partial substitution of Ge in 30BaO–15TiO2–55GeO2 (BTG55) by Si. The BTGS25 satisfied both thermal stability for fiber drawing and electronic polarizability for nonlinear optical property. After crystallization, the BTGS25 bulk crystallized glass showed surface crystallization behavior with the polar c-orientation of fresnoite phase, which was favorable for large second-order optical susceptibility. Following the results of the bulk glass, we prepared the BTGS25 glass fiber without precipitation of fresnoite crystallites. The BTGS25 crystallized fiber also showed c-oriented surface crystallization of fresnoite and second harmonic generation, which shows that the crystallized fiber is a promising material for fiber-type optical active devices.