In this study, we synthesized two different silica monoliths by using sol-gel, solvent exchange, surface modification, ambient pressure drying processes, and surfactant-based templating technique followed by calcination process. All of the prepared two silica monoliths showed crack-free appearance with fairly good transparency, and furthermore were confirmed to have extremely high porosity, specific surface area, and mean pore size below 30 nm. The silica aerogel sample exhibited finer and more homogeneous nano-sized pore structure due to spring back effect caused by surface modification, which resulted in better thermal insulation performance. Based on measured thermal conductivities and theoretical relationship, multi-layered glass window system in which silica monolith prepared in this study was inserted as a middle layer was revealed to have superior thermal insulation performance compared to conventional air-inserted glass window system.