Photopolymerization　of　acrylated　poly(ethylene　glycol)　prepolymers　is　a　facile　method　for　high-efficiency　carbon　capture　membrane　fabrication.　However,　the　oxygen　intolerance　of　the　free　radical　reaction　demands　oxygenfree　condition　for　membrane　fabrication,　which　hampers　the　potential　scale-up　membrane　manufacture.　In　this　work,　a　brand　new　method,　called　thiol-olefin　click　reaction　coupled　high-viscosity　solution,　was　proposed　for　in-air　preparation　of　crosslinked　polyethylene　oxides　(PEO)　membranes.　The　thiol-olefin　click　reaction　plays　the　role　of　consuming　the　oxygen　molecules　and　high-viscosity　solution　functions　as　a　barrier　to　hinder　oxygen　diffusion.　Collaboratively,　the　active　oxygen　content　can　be　significantly　diminished,　rendering　the　smooth　reaction　for　crosslinked　PEO　membrane　preparation.　After　optimizing　the　component　of　the　casting　solution,　i.e.,　tailoring　the　membrane　microstructure,　the　optimal　PEO　membrane　offers　a　CO2　permeability　of　550　Barrer,　with　a　CO2/N2　selectivity　of　52.　Moreover,　the　membrane　can　stably　run　for　120　h.　Thus,　our　study　provides　an　innovative　approach　for　convinient　and　rapid　construction　of　high-performance　crosslinked　PEO　membranes　in　air.