Conjugated microporous polymers (CMPs) are a kind of polymeric materials combining both high porosities and photoelectric functions and are applied in numerous fields. Herein, three CMPs are facilely synthesized through cationic cyclization polymerization of monomers with multiple enediyne moieties. The chemical structures of the CMPs were characterized with solid-state C-13 cross-polarization/magic-angle spinning NMR spectroscopy and Fourier transform infrared spectroscopy. The obtained CMPs exhibit high Brunauer-Emmett-Teller specific surface areas (up to 780 m(2) g(-1)) and excellent adsorption functionality. The highest uptake capacities are up to 12.7 wt % for carbon dioxide (1.0 bar, 273 K) and 246 wt % for iodine (353 K), which are superior to those of most porous organic polymers (POPs). We believe that this metal-free strategy will provide a novel approach toward the synthesis of CMPs and would further expand the application scope of POPs.