This study employed tetraethyl orthosilicate (TEOS) and Y(NO3)3·6H2O as precursors to synthesize Y2O3-SiO2 composite aerogels via sol-gel combined with ethanol supercritical drying technology. The influence of ammonia (NH4OH) and propylene oxide (PO) as gelation initiators on the structure and properties of Y2O3-SiO2 composite aerogels was investigated. Following calcination at 1100 °C, the specific surface areas of Y2O3-SiO2 composite aerogels prepared with ammonia and propylene oxide as gelation initiators were found to be 128.84 m2/g and 25.33 m2/g, respectively. Notably, aerogels prepared using ammonia as the gelation initiator exhibited enhanced high-temperature phase and structural stability. To overcome the brittleness and low strength associated with aerogels, mullite fibers were incorporated into Y2O3-SiO2 aerogels using a vacuum impregnation process, resulting in Y2O3-SiO2 aerogel fiber composites. The thermal conductivity of the Y2O3-SiO2 aerogel composites was as low as 0.092 W/m−1·K−1 at 1000 °C, significantly lower than that of 0.135 W/m−1·K−1 for the SiO2 aerogel fiber composites. Due to the high specific surface area and thermal stability, Y2O3-SiO2 aerogel fiber composites demonstrate promising potential as thermal insulation materials suitable for diverse applications in the aerospace industry.