We report a significant advance in thermally insulating transparent materials: silica-based monoliths with controlled porosity which exhibit the transparency of windows in combination with a thermal conductivity comparable to aerogels.The lack of transparent, thermally insulating windows leads to substantial heat loss in commercial and residential buildings, which accounts for similar to 4.2% of primary US energy consumption annually. The present study provides a potential solution to this problem by demonstrating that ambiently dried silica aerogel monoliths, i.e., ambigels, can simultaneously achieve high optical transparency and low thermal conductivity without supercritical drying. A combination of tetraethoxysilane, methyltriethoxysilane, and post-gelation surface modification precursors were used to synthesize ambiently dried materials with varying pore fractions and pore sizes. By controlling the synthesis and processing conditions, 0.5-3 mm thick mesoporous monoliths with transmittance >95% and a thermal conductivity of 0.04 W/(m K) were produced. A narrow pore size distribution, <15 nm, led to the excellent transparency and low haze, while porosity in excess of 80% resulted in low thermal conductivity. A thermal transport model considering fractal dimension and phonon-boundary scattering is proposed to explain the low effective thermal conductivity measured. This work offers new insights into the design of transparent, energy saving windows.