The trade-off relationship between permeability and selectivity as well as plasticization issues have largely impeded the advancement of membrane technology. Mixed-matrix-membranes (MMMs) with the incorporation of fillers into the polymer matrix is one promising method to deal with these challenges by carefully tuning their chemical properties. Compared with nanoparticles, the counterpart of nanosheet has a larger external surface area with a tendency to have closer contact with a polymer matrix to form a defect-free membrane at higher loading. This work successfully synthesized a high aspect ratio (30/1) of KAUST-8 nanosheets with high CO2 uptake (60 cm3/g). This enables an optimal loading of 30 wt.% in the CO2-attractive crosslinked poly(ethylene oxide) (XLPEO) membrane and results in the simultaneously enhanced CO2 permeability and CO2/N2 selectivity with 280 % and 30 % up, respectively in the mixed gas permeation measurements (50/50 vol.). The resultant membrane performance surpassed the 2008 Robeson upper bound. Meanwhile, the stabilized MMM performance of up to 6 bar and high thermal stability of up to 350 °C bring extra benefits to the KAUST-8-based XLPEO membrane for post-combustion flue gas treatment.