In spite of the wide use of alkylamine (AA) surfactants, little attention has been paid to their spontaneous reactivity in air. Exposure of AA surfactants to CO2 results in the formation of alkylammonium-alkylcarbamate (AAAC) molecular pairs. The effect of hydrocarbon chain length on the reactivity of AAs was followed by monitoring mass gain vs time under atmospheric conditions as well as in a saturated CO2 environment. The rates of conversion to AAAC decreased with hydrocarbon chain length. Indexed powder X-ray diffractograms and the corresponding unit cells are presented for all phases of AAs and AAACs with chain lengths of 14, 16, and 18 carbons. Temperature-resolved powder X-ray diffraction of AAACs indicated anisotropic thermal expansion occurring exclusively along the a direction of the unit cell.