A flexible and free standing conjugated microporous polymer (CMP) membrane was prepared using a polyvinylpyrrolidone (PVP) electrospun membrane as a template. The PVP nanofibers of the template membrane were coated with a thin layer of the CMP through the in situ Sonogashira-Hagihara coupling reaction of 1,3,5-triethynylbenzene and 1,4-diiodobenzene. The PVP nanofibers were removed by the solvent extraction to produce the CMP membrane, which retained the entangled fibrous structure of the template membrane. Each fiber showed a hollow tubular structure having a CMP wall with a thickness of tens of nanometers. The microporous polymer membrane exhibited a high BET surface area with hierarchical porosity and good permeability. As a catalytic CMP membrane, the Ag nanoparticle-immobilized microporous polymer membrane was fabricated using an electrospun PVP@Ag membrane as a template. After being coated with the CMP, the PVP nanofibers were removed by the solvent extraction, but the Ag nanoparticles were trapped in the microporous polymer shell. The catalytic CMP membrane was successfully used for the catalytic reduction reaction of 4-nitrophenol. The hollow tubular structure and hierarchical porosity of the membrane allowed for the reactants to easily penetrate into the CMP wall and to contact the Ag nanoparticles, resulting in the high catalytic activity.