Recently, the emergence of conductive metal-organic frameworks (MOFs) has given great prospects for their applications as active materials in electronic devices. In this work, a high-quality, free-standing conductive MOF membrane was prepared by an air-liquid interfacial growth method. Accordingly, field-effect transistors (FETs) possessing a crystalline microporous MOF channel layer were successfully fabricated for the first time. The porous FETs exhibited p-type behavior, distinguishable on/off ratios, and excellent field-effect hole mobilities as high as 48.6 cm V s, which is even comparable to the highest value reported for solution-processed organic or inorganic FETs.

Lithium–sulfur (Li–S) batteries are appealing candidates for next‐generation high‐energy rechargeable batteries, but practical applications are still limited by poor cyclic life, which is caused by severe polysulfide shuttling in high‐sulfur‐loading batteries. Herein, a facile route is presented to fabricate high‐performance Li–S batteries using a crystalline microporous membrane, which is prepared using a conductive metal–organic framework (MOF) material. With ordered microporous structure, large specific surface area, good sulphiphilicity, and excellent conductivity, the MOF membrane is grown in situ on the commercial separator and is an ideal light‐weight barrier (0.066 mg cm−2) for suppressing the polysulfide shuttling, which can significantly promote the capacities, rate capabilities, and cycling stabilities of Li–S batteries. Taking the advantage of this functional separator, the high‐sulfur‐loading Li–S battery (8.0 mg cm−2 and 70 wt% of sulfur in cathode) delivers a high area capacity of 7.24 mAh cm−2 after 200 cycles, thus providing a promising path toward advanced Li–S batteries.