Metal organic framework (MOF)-based adsorptive membranes are attractive materials in high flux separation and/or in abatement of hazardous materials. However, fabrication of continuous MOF membrane with ultra-high loading and anti-solvent property is a challenging task. Here, the authors report a coordination replication synthetic approach via a morphological replacement procedure that employs pre-shaped Al2O3 microfiltration membrane to produce freestanding MOF multifunctional membrane (FMMMs). The authors achieve precise control of crystal size, morphology, and orientation on the FMMMs. Moreover, the intrinsic porous structure inherited from Al2O3 pre-fabricated membrane and newly introduced MOF active sites synergistically contribute to a great rejection (99%) of organic dyes from organic solvent with a permeability over 175 L m−2 h−1 bar−1. Furthermore, the as-synthesized FMMMs enable heterogeneous HCHO catalytic oxidation and extremely rapid 2-chloroethyl ethyl sulfide (CEES) detoxification. This work opens the way to design high-performance FMMMs from pre-shaped membranes for various applications.