Waste foundry sand is a kind of solid wastes produced during casting process, the casting output of China ranks first in the world for many years and the amount of waste foundry sand is huge. But the utilization rate of the waste foundry sand is low in China. It is not only a threat to the environment but also a waste.In this paper, waste foundry sand was taken as main starting material, adding proper amount of additives. The shaped samples were heated in the electric oven at the temperature of 1300°C, 1400°C and 1500°C respectively, the soaking time is 3h for all samples.The microstructure and phase composition of the samples were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). The effect of the temperature on the synthesis of mullite-silica-rich glass was investigated. The results showed that the main phases were mullite and glass when the samples were heated at 1500°C, mullite grain grew well and formed network structure. This network was benefical to improve the thermal shock resistence.It opens up a new method to utilize the waste foundry sand.