We present for the first time the CO2 capture and in-situ conversion into bicarbonate as a carbon-bearing product using an amine with built-in surface activity. The surface-active amine was 3-(dimethylamino)propylamine (DMAPA) modified with propylene oxide (PO) groups (DMAPA-xPO, x = 4, 6, 8, 12). Analysis of the CO2 capture capacity data with 13C Nuclear Magnetic Resonance (NMR) spectroscopy determined the bicarbonate concentrations and the generation mechanism during the CO2 capture influenced by the PO groups, establishing a relationship between CO2 solubility, pH of the solution, and steric effect. Results demonstrated the effectiveness of the built-in surface activity with an optimal PO level (DMAPA-6PO). DMAPA-6PO enhanced the bicarbonate generation by 54%, in comparison to DMAPA, under ambient conditions.