Abstract: | Metal–organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass‐transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet‐based membranes remain as great challenges. A modified soft‐physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub‐10 nm‐thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H2/CO2 separation performance, with a separation factor of up to 166 and H2 permeance of up to 8×10?7 mol m?2 s?1 Pa?1 at elevated testing temperatures owing to a well‐defined size‐exclusion effect. This nanosheet‐based membrane holds great promise as the next generation of ultrapermeable gas separation membrane. |