A simple, mild, and effective template approach has been used to produce hollow silica nanospheres with controlled sizes ranging from 40 to 150 nanometers. The obtained powders showed systematic variations in measured thermal conductivity, with values down to 0.024 W/(mK) so far, with en expressed goal to reach below 0.020 W/(mK). Surface hydrophobization was successfully performed. Thus, hollow silica nanospheres are considered to be promising building blocks for new hydrophobic, superinsulating materials.