Porous organic polymers have recently received great attention because of their promising applications in the removal of thiophene compounds in liquid fuels and for the nuclear waste (such as radioactive iodine isotopes) treatments. Herein, a series of conjugated mesoporous hyper-cross-linked polymers (CMHPs) were prepared through our newly developed silicon-promoted cationic polymerization in a straightforward manner. The CMHPs exhibited extended π-conjugation, intrinsic porosity, high surface area, and excellent physicochemical stability. They showed an outstanding dibenzothiophene uptake capacity of ∼1335 mg g-1, which far exceeded many reported porous organic polymers. Meanwhile, these CMHPs showed high adsorption capacity for iodine vapor. Altogether, the CMHPs prepared by the facile and metal-free cationic reactions have great potential in adsorption of harmful substances and environmental protection.