We present combined results of optical, scattering, and spectroscopic studies of (K2O)15(Nb2O5)15(TeO2)70 glass and glass ceramic and comment on possible mechanisms of the optical behavior in terms of existing theory. The glass ceramic is confirmed to generate second-harmonic light. Combined neutron and X-ray diffraction data have been indexed to an orthorhombic unit cell (a = 3.39 A, b = 4.78 A, c = 6.38 A). Additionally, we show that the previously proposed fluorite-based model is insufficient for the crystal phase using real-space analysis. The orthorhombic unit cell allows the possibility of a conventional explanation for the second-harmonic generation (SHG). Peak broadening and scattering length difference analyses are combined to formulate a model of anion disorder in the crystal phase. TEM and SAXS reveal domains of ≈15 nm in both the glass and glass ceramic. The role of liquid−liquid phase separation in the crystallization behavior of this material is discussed. Solid-state 93Nb MAS NMR and Raman ...