Fused cast Al2O3-ZrO2-SiO2 (AZS) refractory is the key building material of glass furnace. Calcined aluminum oxide powder and ordinary industrial aluminum oxide powder were used as raw materials to prepare fused cast AZS refractories, respectively. The structure and properties of the two fused cast AZS refractories were compared and analyzed by lithofacies analysis, X-ray diffraction analysis, and energy dispersive spectroscopy analysis, etc. The results indicate that fused cast AZS refractory material prepared by ordinary industrial aluminum oxide powder has the incomplete conversion γ-Al2O3, which leads to uneven distribution of Al2O3-ZrO2 eutectic. The alumina phase in the fused cast AZS refractory prepared by calcined alumina oxide powder is α-Al2O3. The fused cast AZS refractory prepared by calcined aluminum oxide has less baddeleyite, more Al2O3-ZrO2 eutectic and more uniform distribution of glass phase. The distribution of crystal structure affects amount of glass phase exudation and corrosion resistance to molten glass. The glass phase exudation of the fused cast AZS refractory prepared by calcined aluminum oxide powder is 0.57 percentage points lower than that of fused cast AZS refractory prepared by ordinary industrial aluminum oxide powder. The corrosion resistance to molten glass of fused cast AZS refractory prepared by calcined aluminum oxide power is 0.15 mm/24 h higher than that of fused cast AZS refractory prepared by ordinary industrial aluminum oxide power.