Reduction　of　CO2　emission　is　an　urgent　global　demand　to　deal　with　the　current　extreme　climate　and　ecosystem　destruction.　Polyethylene　oxide　(PEO)　is　an　ideal　material　for　CO2　separation　membranes,　because　of　its　mod-erate　affinity　for　CO2.　However,　due　to　its　high　tendency　of　crystallization,　the　mass　transfer　of　CO2　is　significantly　hampered,　resulting　in　poor　separation　performance.　This　study　proposed　of　employment　of　trehalose　as　the　filler　to　PEO　membrane　with　subsequent　thermal　annealing,　that　is　hydrogen-bond　suppression　crystalliza-tion　coupling　thermal　annealing　healing　defects　strategy,　to　simultaneously　enhance　the　gas　transport　and　selectivity.　The　trehalose　plays　the　role　of　suppressing　PEO　crystallization　while　thermal　annealing　charges　for　healing　defects.　Consequently,　the　optimized　trehalose-loaded　PEO　membrane　exhibits　a　CO2　permeability　of　117　Barrer　and　an　ideal　CO2/N2　selectivity　of　51,　which　is　superior　to　the　pure　PEO　membrane.　Moreover,　the　membrane　offers　merits　of　anti-plasticization　feature　and　long-term　running　stability.