High-efficiency　CO2　capture　has　become　increasingly　vital　for　alleviating　the　ongoing　global　temperature　which　leads　to　severe　impacts　on　virtually　every　aspect　of　human　life.　Thin-film　composite　membranes　(TFCM)　have　attracted　growing　attention　for　conducting　CO2　capture,　owning　to　their　energy-efficient　and　environment-friendly　merits.　However,　the　nonideal　interface　between　the　gutter　layer　and　the　separation　layer　hampers　the　fabrication　of　defect-free　and　thin　separation　layer,　which　renders　low　separation　performance.　In　this　work,　we　developed　a　strategy,　i.e.,　coupling　the　oxygen-plasma　modification　with　spin-coating,　for　engineering　the　interface　between　the　gutter　layer　and　separation　layer　of　TFCM.　Leveraging　this　idea,　the　TFC　membrane,　consisting　polydimethylsiloxane　(PDMS)　served　as　the　gutter　layer　and　poly　(ether-block-amide)　(PEBA)　as　the　thin　separation　layer,　was　manufactured　by　conveniently　spin-coating　PEBA　solution　on　the　oxygen-plasma-treated　PDMS　layer.　The　optimized　PEBA-based　TFCM　membrane　realized　superior　separation　performance,　e.　g.,　a　CO2　permeance　of　2011　GPU,　a　CO2/N2　selectivity　of　24,　and　100-hour　stably　running,　which　outperformed　most　of　the　reported　PEBA-based　TFCM.　Thus,　the　interface　engineering　strategy　proposed　in　this　study　opens　a　new　door　for　rational　fabrication　of　high-performance　TFCM.