Separation of p‐xylene (kinetic diameter ca. 0.58 nm) from its bulkier isomers (o‐xylene and m‐xylene, ca. 0.68 nm) is challenging, but important in the petrochemical industry. Herein, we developed a highly selective and stable metal–organic framework (MOF) MIL‐160 membrane for selective separation of p‐xylene from its isomers by pervaporation. The suitable pore size (0.5∼0.6 nm) of the MIL‐160 membrane selectively allows p‐xylene to pass through, while excluding the bulkier o‐xylene and m‐xylene. For the separation of equimolar binary p‐/o‐xylene mixtures at 75 °C, high p‐xylene flux of 467 g m−2 h−1 and p‐/o‐xylene selectivity of 38.5 could be achieved. The stability of MIL‐160, ensured the separation performance of the MIL‐160 membrane was unchanged over a 24 h measurement. The high separation performance combined with its high thermal and chemical stability makes the MIL‐160 membrane a promising candidate for the separation of xylene isomers.