Crystallization and microstructural behavior of various strontium-rich glass ceramics in the system 65[(PbxSr1−x)TiO3]-24[2SiO2⋅B2O3]-5[BaO]-5[K2O]-1[La2O3] (0.0≤𝑥≤0.4) with addition of 1% La2O3 have been investigated. The addition of La2O3 has been found to play an important role in crystallization of perovskite (Pb,Sr)TiO3 as a solid solution phase. Also, it causes a change in the surface morphology of the fined crystallites of the major phase. Differential thermal analysis (DTA) shows only one exothermic crystallization peak, which shifts towards higher temperature with increasing amount of strontium oxide. Glasses were subjected to various heat treatment schedules for the crystallization. Very good crystallization of strontium-rich glass compositions is observed. X-ray diffraction studies confirm that cubic perovskite lead strontium titanate crystallizes as major phase. Lattice parameter decreases with increasing strontium content similar to lead strontium titanate ceramics. Uniform and interconnected crystallites are dispersed in glassy matrix.