Abstract The emerging sub−1 nm nanowires (SNWs) have received tremendous attention given their intriguing properties and broad applications attributable to their ultrasmall feature size. However, applying SNWs in microstructure‐preserving macroscopic functional materials (e.g., aerogels) remains challenging because the solvents used for preparing SNWs are not compatible with conventional supercritical drying or freeze‐drying techniques. In this study, the fabrication of SNW aerogels (SNWAs) is pioneered by developing a nonpolar solvent‐based freeze‐casting strategy. Cyclohexane, a nonpolar solvent with a freezing point (6.5 °C) comparable to that of water, is selected as a reaction and drying medium to assemble various SNWs. The resulting self‐standing SNWAs display low density, excellent hydrophobicity and lipophilicity, and tunable luminescent color. This strategy not only introduces a new aggregation form of SNWs but also provides a creative perspective on synthesizing aerogel structures from sub−1 nm building blocks.