A novel strategy to design a high-performance composite membrane for CO2 capture via coating a thin layer of water-swellable polymers (WSPs) onto a porous support with enriched CO2-philic groups is demonstrated in this study. First, by employing a versatile platform technique combining non-solvent-induced phase separation and surface segregation, porous support membranes with abundant CO2-philic ethylene oxide (EO) groups at the surface are successfully prepared. Second, a thin selective layer composed of Pebax MH 1657 is deposited onto the support membranes via dip coating. Because of the water-swellable characteristic of Pebax and the enriched EO groups at the interface, the composite membranes exhibit high CO2 permeance above 1000 GPU with CO2/N2 selectivity above 40 at a humidified state (25 °C and 3 bar). By tuning the content of the PEO segment at the interface, the composite membranes can show either high CO2 permeance up to 2420 GPU with moderate selectivity of 46.0 or high selectivity up to 109.6 with fairly good CO2 permeance of 1275 GPU. Moreover, enrichment of the PEO segment at the interface significantly improves interfacial adhesion, as revealed by the T-peel test and positron annihilation spectroscopy measurement. In this way, the feasibility of designing WSP-based composite membranes by enriching CO2-philic groups at the interface is validated. We hope our findings may pave a generic way to fabricate high-performance composite membranes for CO2 capture using cost-effective materials and facile methods.