Waste aluminum slag and clay were used as raw materials to prepare mullite-corundum composites. The influences of different Al2O3/SiO2 ratios on the crystalline phases were discussed. XRD and SEM techniques were used to characterize the crystalline phases. The results show that sintering temperature can significantly change the crystalline phases and their amount. Two crystals mullite solid solution and corundum were formed in each sample. Mullite solid solution has two compositions: Al4.544Si1.4560O9.728 and Al4.59Si1.41O9.70. The amount of mullite increases with sintering temperature increasing, and reaches to the highest 100% at 1650 degrees C. SEM observation shows that mullite takes needle-like or column shapes which indicates good properties of materials.