Abstract: The effect of Cr₂O₃ on the nucleation and crystallization of Na₂O-CaO-Al₂O₃-SiO₂-F^- glass has been investigated by means of ESR(Electron Spin Resonance), SEM(Scanning Electron Microscope), EDS(Energy Dispersive Specrometer) and so on. Computer pattern recognition is applied to optimize the heat-treatment schedules. The experimental results show that the base glass containing more than 1.5 % (mass fraction) Cr₂O₃ can be nucleated internally and converted to spheroidal crystal glass materials. The spheroidal crystal consisted of fibrous wollastonite crystals radiating from a center. The residual glass phase filled in the interstices between the fibers and between the spherulites. During heat treatment process, the valence states ofchromium changed from Cr^6- to Cr^3-, and the Cr-spinel solidsolution CaCr₂O₄ precipitated followed this valence change. At the primary stage of crystallization, the Cr-spinel could act as a nucleating center on which the principal orstalline phase β-CaSiO₃ grew epitaxially.