Against the background of global energy shortages and the need for long-term flight safety of aerospace vehicles, traditional silica aerogels have the problems of insufficient temperature resistance and poor thermal insulation at high-temperatures, and are no longer able to meet the demand. In this study, a series of monolithic Al2O3Y2O3SiO2 ternary aerogels were successfully synthesized via synchronous sol–gel and ethanol supercritical drying. Both the prepared aerogels and the calcined samples at 1000 °C exhibited a complete three-dimensional network structure and a high specific surface area (up to 675.7 m2/g and 214.4 m2/g), which was attributed to the supporting effect of the Al2O3 component on the overall skeleton and the inhibiting effect of the Y2O3 component on the crystal transformation. Mullite fiber reinforced Al2O3Y2O3SiO2 aerogel composites were synthesized by vacuum impregnation using mullite fiber felt as a matrix. The prepared sample exhibit very low thermal conductivity (as low as 0.079 W⋅m−1·K−1 at 1000 °C). In summary, the good structural stability and high temperature thermal insulation performance make Al2O3Y2O3SiO2 ternary aerogel have the potential of efficient service in more application scenarios. This study provides a product optimization reference idea for the thermal insulation material industry.