The study explores the use of single-component water-lean solvents, particularly N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA), for CO₂ capture. It finds that these solvents self-assemble into tetrameric clusters, which enable cooperative and stepwise CO₂ capture. This process involves the formation of carbamic acid and its derivatives, such as carbamic anhydride and alkoxy carbamic anhydrides, under mild conditions. The tetrameric clusters provide a shielded reactive site, facilitating the formation of these unusual adducts. The study uses a combination of experimental techniques, including NMR spectroscopy and theoretical calculations, to elucidate the molecular and supramolecular interactions during self-assembly and CO₂ absorption. The findings suggest that the tetrameric clusters can enhance the CO₂ storage capacity and provide a means for carbamates to act as initiators for future oligomerization or polymerization of CO₂. This work opens new avenues for the development of more efficient and cost-effective CO₂ capture technologies.The study explores the use of single-component water-lean solvents, particularly N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA), for CO₂ capture. It finds that these solvents self-assemble into tetrameric clusters, which enable cooperative and stepwise CO₂ capture. This process involves the formation of carbamic acid and its derivatives, such as carbamic anhydride and alkoxy carbamic anhydrides, under mild conditions. The tetrameric clusters provide a shielded reactive site, facilitating the formation of these unusual adducts. The study uses a combination of experimental techniques, including NMR spectroscopy and theoretical calculations, to elucidate the molecular and supramolecular interactions during self-assembly and CO₂ absorption. The findings suggest that the tetrameric clusters can enhance the CO₂ storage capacity and provide a means for carbamates to act as initiators for future oligomerization or polymerization of CO₂. This work opens new avenues for the development of more efficient and cost-effective CO₂ capture technologies.