Metal-induced ordered microporous polymers (MMPs), a class of porous polymer, are synthesized from amine-bearing polymers, small organic linkers and divalent metal ions using a polymer-directed chemical synthesis process. Specifically, small organic linkers first coordinate to metal ions, with the resulting unit cells then self-assembling along the extension of polymer chains to construct three-dimensional frameworks. The MMPs demonstrate good controllability of crystal and framework size, as well as hydrolytic stability. MMP dispersions were coated on a modified polysulfone substrate to fabricate MMP/mPSf membranes with an ultrathin selective layer (below 50 nm) and surface areas of > 100 cm(2). The MMPs are readily fabricated into defect-free thin selective-layered membranes with high CO2 permeance (3,000 GPU) and stable CO2/N-2 selectivity (78) under both humid and dry gas feed conditions, demonstrating promising CO2 membrane separation performance. This synthetic methodology could be extended to other polymers, potentially enabling facile synthesis of membrane materials.