Barium aluminosilicate glasses are being investigated as matrix materials in high-temperature ceramic composites for structural applications. Kinetics of crystallization of two refractory glass compositions in the barium aluminosilicate system have been studied by differential thermal analysis (DTA), x-ray diffraction (XRD), and scanning electron microscopy (SEM). From variable heating rate DTA, the crystallization activation energies for glass compositions (wt. %) 10BaO–38Al2O3–51SiO2–1MoO3 (glass A) and 39BaO–25Al2O3–35SiO2–1MoO3 (glass B) were determined to be 553 and 558 kJ/mol, respectively. On thermal treatment, the crystalline phases in glasses A and B were identified as mullite (3Al2O3 · 2SiO2) and hexacelsian (BaO · Al2O3 · 2SiO2), respectively. Hexacelsian is a high-temperature polymorph which is metastable below 1590 °C. It undergoes structural transformation into the orthorhombic form at ∼300 °C accompanied by a large volume change which is undesirable for structural applications. A process needs to be developed where stable monoclinic celsian, rather than hexacelsian, precipitates out as the crystal phase in glass B.