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Based on the measurement of viscosities and critical temperatures of CaO-MgO-SiO₂- Al₂O₃-B₂O₃ slag system with various B2O3 contents, the slag with higher than 15 mas. % Al₂O₃ content has the lowest critical temperature and the widest solid-liquid coexisting region at about 2,0 mas. % B₂O₃. Furthermore, the X-ray diffractometer (XRD) result verified that bechilites whose melting point are low forms. Raman spectra revealed that the effect of network forming on viscosity is smaller than the effect of bechilites, which leads to the slag viscosity decrease with B₂O₃ addition. Base on the above research, so ludwigite can meet the requirements of a BF welding flux to decrease the critical temperature and improve the fluidity of the high Al₂O₃ slag.