In this work, we deposited a CO2-selective block copolymer, Pebax-1657, as a selective layer with a thickness of 2-20 nm on the oxygen plasma-activated surface of poly(dimethylsiloxane) (PDMS) used as a gutter layer (thickness ∼400 nm). This double-layered structure was subsequently transferred onto the polyacrylonitrile (PAN) microporous support and studied for CO2/N2 separation. The effect of interfacial molecular arrangements between the selective and gutter layers on CO2 permeance and selectivity has been investigated. We have revealed that the gas permeance and selectivity do not follow the conventional theoretical predictions for the multilayer membrane (resistance in series transport model); specifically, more selective CO2/N2 separation membranes were achieved with ultrathin selective layers. Detailed characterization of the chemical structure of the outermost membrane surface suggests that nanoscale blending of the ultrathin Pebax-1657 layer with O2 plasma-activated PDMS chains on the surface takes place. This nanoblending at the interface between the selective and gutter layers played a critical role in enhancing the CO2/N2 selectivity. CO2 permeances in the developed thin-film composite membranes (TFCM) were between 1200 and 3500 gas permeance units (GPU) and the respective CO2/N2 selectivities were between 72 and 23, providing the gas separation performance suitable for CO2 capture in postcombustion processes. This interpenetrating polymer interface enhanced the overall selectivity of the membrane significantly, exceeding the separation ability of the pristine Pebax-1657 polymer.