We report a new SBN-tellurite ceram-glass system, where the [(SrO)(y)(BaO)(1−y) (Nb2O5)](1−x) (SBN) ferroelectric crystallites precipitate on a tellurite (TeO2)x glass surface with nominal compositions x < 0.8 and y = 0.6 to 0.75. X-ray diffraction, calorimetry, and electro-optic measurements confirmed the ferroelectric nature of the SBN crystallites. In principle, this system has the potential for high transparency and the property tunability to match the application needs of optical devices.