Solid‐state electrolytes hold great promise for lithium‐based batteries with high energy density and safety. Here, novel metal‐organic frameworks (MOFs) based composite membranes were fabricated by a rolling process and subsequently employed as quasi solid‐state electrolytes, exhibiting improved ionic conductivity and Li+ transference number as well as stable electrochemical window. Furthermore, the MOF‐based membranes presented a significant effect in modulating the stripping/plating process of Li and resulted in a dendrite‐free Li deposition. The corresponding LiFePO4|Li batteries were assembled and presented improved rate capability and high Coulombic efficiency, offering a new option for MOF‐based electrolytes. [ABSTRACT FROM AUTHOR]