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0.5LiMnO2-0.5B2O3 glass has been prepared by quenching a melt of LiNO3, MnO2 and B2O3 at 1100°C to room temperature in air. The crystallization mechanism of this kind of glass was investigated by differential thermal analysis (DTA) and powder X-ray diffraction (XRD). It is shown that the substances crystallized from powder and bulk samples are different because manganese with lower valence in powder sample can be further oxidized by the oxygen penetrated through the large surface of powder sample. For a powder sample the glass transition endothermic peak in the DTA curve is overlapped by an exothermic reaction attributed to the oxidization of Manganese. LiMn2O4 can not be crystallized directly from the glass matrix but can be formed on the surface of glass particles by effect of oxygen in air near the glass transition temperature.