Since they were first prepared in 1931 via supercritical drying (SCD), [1] aerogels have been utilized for rather specific applications in spite of their wide range of extraordinary properties, such as high optical transparency (> 90 %), large surface areas (ca. 1000 m 2 g -1 ), low refractive indices (< 1.01), high thermal and acoustic insulation values, and low dielectric constants (ca. 1.1). An aerogel-based Cherenkov detector has been used to detect charged elementary particles, thus contributing to the development of high-energy physics. [2,3] In the field of space development, [4] the first aerogel cosmic dust collector was launched on February 7, 1999 and returned to Earth on January 15, 2006, successfully bringing back the dust of the comet "Vilt 2" after a seven-year journey.[5] Despite these applications, aerogels are not routinely found in our daily life because they collapse easily and are difficult to prepare in a large-scale industrial setting. The unique characteristics of aerogels stem from the fact that they are composed mostly of air. As the skeletons that comprise their porous morphology are too thin, aerogels are brittle, and they must be dried with the utmost care by using SCD, for example, to preserve their fragile pore structure. To overcome such challenges for silica-based aerogels, numerous attempts to strengthen the gel skeletons by aging, [6,7] crosslinking with organic polymers, [8][9][10] modifying surfaces hydrophobically, [11][12][13] and conventional drying [14,15] have been explored.Prakash et al. [13] have obtained aerogel films with porosity up to 98.5 % by adding hydrophobicity through the use of trimethylchrolosilane constituents on bare silica networks. This method enables the so-called spring-back phenomenon, in which temporarily shrunk gel networks recover their original forms like a sponge. Another prevalent approach is to use trifunctional silicon alkoxides together with conventional tetrafunctional silicon alkoxides such as tetramethylorthosilicate (TMOS) or tetraethylorthosilicate (TEOS) in a sol-gel route. [16,17] Incorporating trifunctional monomers with one hydrophobic group, such as alkyltrialkoxysilanes, also makes the resultant gel surface hydrophobic [18,19] but sacrifices the transparency aspect. [20] As silanol groups that are closely located to each other lead to persistent shrinkage by forming siloxane bonds during drying, [21] incorporating hydrophobic groups to reduce the chances of such condensations prevents persistent shrinkage. The repulsive interactions between hydrophobic moieties also promote the spring-back effect. An in situ treatment of alkyltrialkoxysilanes rather than a post treatment by a silane coupling agent on bare silica is an effective way to achieve hydrophobicity in a simple manner. However, trifunctional alkoxides usually form cyclic and cagelike closed species that hinder the homogeneous gelling of a starting solution, especially when the monomer concentration is low (unfortunately in aerogel preparation, monomer concentration must be ...