A new photoinitiating system for the metal-free preparation of conjugated microporous polymers (CMPs) is reported. In this approach, irradiation of solutions containing an electroactive monomer, possessing both carbazole and fluorene units, 9,9'-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis-9H-carbazole (CFD), and the iodonium salt (Ph2I+PF6-) as the oxidizing agent resulted in the formation of CMPs. Photoinduced step-growth polymerization proceeded through the successive electron transfer between the excited CFD and iodonium salt, proton release, and coupling reactions. The polymers formed were characterized by FT-IR and H-1 NMR analyses. The electrochemical and optical properties of CMPs before and after the dedoping process were evaluated by cyclic voltammetry, differential pulse voltammetry, and UV-vis absorption and photoluminescence techniques. The porous structure of the obtained polymers was confirmed by atomic force microscopy and scanning electron microscopy studies.