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We have measured the Raman spectra of β- and α-barium metaborate in crystal and liquid states from room temperature to 1873K, with a semiconductor laser as the laser source, coupled with a time-resolved detection system to eliminate the dense thermal emission background when temperature was considerably high.Temperature-dependent Raman spectra can clearly indicate that the phase transformation from β- to α-barium metaborate has been completed during 1273 - 1300 K. Variations of different kinds of microstructure units with temperature are identified and discussed.