To enhance CO2 sorption efficiency under low-pressure conditions and effectively compete with N2 sorption in flue gas, modifications are implemented aimed at improving the adsorption capacity and selectivity of ZIF-8, renowned for their robust stability. Deep eutectic solvent (DES) comprising tetraethylammonium chloride (TEAC), tetrapropylammonium chloride (TPAC), and tetrabutylammonium bromide (TBAB) as hydrogen-bond acceptors, along with ethanolamine (MEA) as the hydrogen-bond donor, were meticulously prepared for this purpose. ZIF-8 underwent modification through DES loading, resulting in the distinctive emergence of a “core-membrane” structure. Characterization revealed that the DES effectively adhered to the surface of ZIF-8 in a membrane-like structure, without altering the chemical structure or pore size of ZIF-8. The most significant enhancement in sorption capacity was observed with TPAC&MEA modification. Considering the presence of N2 partial pressure in the flue gas, at 0.05 and 1 bar, the CO2 adsorption capacities reached 1.92 and 3.03 mmol g−1, respectively, increasing 71.11 and 4.00 times compared to pristine ZIF-8. The ZIF-8 exhibited a CO2/N2 separation coefficient of 72.77, which increased to a maximum of 997.50 after DES modification. Additionally, the modified material demonstrated exceptional cyclic and thermal stability during testing. This study significantly elevates the CO2 adsorption capacity and selectivity of solid materials within the low-pressure range, providing pivotal support for CO2 capture and decarbonization efforts.