Shock compression experiments were performed on samples of 0.13 g/cm3density silica aerogel. The aerogel is a transparent, homogeneous, open cell, SiO2, glass structure with a pore size of 10 nm. A shock velocity of 11.4 km/s was measured at 14.6 GPa (146 kbar) and over sevenfold compression of the specimen, which is threefold expanded relative to the density of crystalline &agr;‐quartz. A shock temperature of nearly 1 eV was measured at 6.7 GPa. These experiments access a new regime for accurate laboratory measurements on high‐temperature, expanded‐volume states of glass.