A series of compounds with an amine based structural motif (ASM) have been synthesized for efficient atmospheric CO(2) fixation. The H-bonded ASM-bicarbonate complexes were formed with an in situ generated HCO(3)(-) ion. The complexes have been characterized by IR, (13)C NMR, and X-ray single-crystal structural analysis. ASM-bicarbonate salts have been converted to pure ASMs in quantitative yield under mild conditions for recycling processes.