A spherical silica aerogel powder with hydrophobic surfaces displaying a water contact angle of 147° was synthesized from a water glass-in-hexane emulsion through ambient pressure drying. Water glass droplets containing acetic acid and ethyl alcohol were stabilized in n-hexane with a surfactant. Gelation was performed by heating the droplets, followed by solvent exchange and surface modification using a hexamethyldisilazane (HMDS)/n-hexane solution. The pH of the silicic acid solution was crucial in obtaining a highly porous silica aerogel powder with a spherical morphology. The thermal conductivity, tapped density, pore volume, and BET surface area of the silica aerogel powder were 22.4 mW·m−1K−1, 0.07 g·cm−3, 4.64 cm3·g−1, and 989 m2·g−1, respectively. Fourier transform infrared (FT–IR) spectroscopy analysis showed that the silica granule surface was modified by Si-CH3 groups, producing a hydrophobic aerogel.