<p>An efficient carbon capture and release system necessitates rapid CO₂ transport to and from active sites, a property typically associated with permanently porous materials featuring large surface areas. Here, we present hydrophobic organic crystals of alkylated monoethanolamine that, despite their nonporous nature, undergo a rapid and reversible solid-to-solid phase transition upon CO₂ uptake and release. Exposure to CO₂ triggers a thermodynamically favored structural rearrangement, enabling quantitative CO₂ capture and forming a stable carbamate, aided by intermolecular interactions involving the long side chains. This process is fully reversible under practical flue-gas CO₂ capture conditions (&gt;0.6% CO₂, 0−100% relative humidity) and enables low-temperature desorption using CO₂ itself as a stripping gas (65 °C at 1 atm CO₂). Structural analysis through in situ XRPD, solid-state NMR spectroscopy, electron diffraction, and Raman analysis confirms that these hydrophobic absorbents selectively uptake CO₂ to form an anhydrous ammonium carbamate pair in the solid state. The non-hygroscopic nature of these organic crystals is exemplified by a representative C10-MEA in the presence of CO_2, resulting in a desorption process with a minimal temperature swing (Δ<i>T</i>_abs-des = 30 °C), offering an energy-efficient (&gt;1.2 GJ/t of captured CO₂) and economically viable alternative for carbon capture applications.</p>