Excessive　CO2　emissions　arising　from　fossil　energy　utilization　pose　severe　threats　to　the　environment,　climate,　and　biological　species.　To　this　end,　high-efficiency　separation　membranes　have　been　developed　to　mitigate　emerging　challenges.　Bisphenol　A　ethoxylate　diacrylate　(BPA)　and　poly(ethylene　glycol)　methyl　ether　acrylate　(PEGMEA)　were　UV-cross-linked　in　the　presence　of　low　molecular　weight　poly(ethylene　glycol)　dimethyl　ether　(PEGDME)　to　prepare　high-performance　CO2　capture　membranes　in　a　green　way.　During　the　entire　membrane　fabrication　process,　no　additional　solvent　was　involved　and　no　waste　of　membrane　materials　occurred,　resulting　in　a　green　process.　The　such-prepared　membrane　presents　an　outstanding　CO2　permeability　of　4883　Barrer,　a　new　record　for　poly(ethylene　oxide)　membranes,　with　a　high　CO2/N-2　ideal　selectivity　of　43　due　to　the　cooperative　contribution　of　BPA　and　PEGDME.　The　unprecedented　separation　performance　of　our　manufactured　membrane　is　even　higher　than　that　of　the　2019　CO2/N-2　upper　bound.　Considering　the　rapid,　cost-effective,　and　green　fabrication　process,　our　membrane　potentially　offers　a　dramatic　advantage　in　alleviating　the　current　greenhouse　gas　issue　and　shows　great　promise　for　practical　applications.