Abstract: In pyrometallurgical process, Al-and Si-bearing minerals in iron and aluminum ores are easily transformed into sodium aluminosilicates in the presence of Na₂O constituents, which alters the leaching behaviors of Al₂O₃ and SiO₂. It was confirmed that sodium aluminosilicates with different phase compositions synthesized at various roasting conditions were effectively digested in the alkaline digestion process. Under the optimum conditions at temperature of 100-120℃, liquid-to-solid ratio (L/S) of 10:2 mL/g, caustic ratio of 4, and Na₂O concentration of 240 g/L, the actual and relative digestion ratio of Al₂O₃ from the synthesized sodium aluminosilicates reached maximums of about 65% and 95%, respectively, while SiO₂ was barely leached out. To validate the superior digestion property of sodium aluminosilicate generated via an actual process, the Bayer digestion of an Al₂O₃-rich material derived from reductive roasting of bauxite and comprising Na_1.75Al_1.75Si_0.25O₄ was conducted; the relative digestion ratio of Al₂O₃ attained 90% at 200℃.