This experimental study describes efficient CO2 capture by 2-amino-2-methyl-1-propanol (AMP)/piperazine (PZ) in ethylene glycol monoethyl ether (EGMEE, 2-ethoxyethanol) containing approximately 15 wt % of water. In these experiments, the solvent is continuously circulated between the absorber (packed-bed reactor at 30, 40, or 45 °C) and the desorber (at 80, 85, or 90 °C). The CO2–solvent reaction equilibria have been investigated by using 13C NMR spectroscopy, which provides confirmatory evidence that the formation of mono- and biscarbamate derivatives of PZ accounts for most of the CO2 absorbed by the AMP/PZ/EGMEE/H2O blend. The solid-state structures of AMP carbamate and of the carbonate salt of protonated AMP have been determined by using XRD. Both AMPCO2− and CO32− species completely convert to the monoalkyl carbonates on dissolving the respective salts in methanol, ethanol, or ethylene glycol.