Hexaphenylbenzene-based porous organic polymers are prepared smoothly through palladium-catalyzed C C coupling polymerization. According to the obtained nitrogen physisorption isotherms, the Brunauer Emmett-Teller-specific surface area for these polymers varies between 742 and 1148 m(2) g(-1). Gravimetric hydrogen adsorption isotherms show that the adsorption capacity for hydrogen is up to 1.5 wt % at 1.13 bar and 77 K Thanks to the propeller-like structure, unique electronic feature, and efficient preparation, hexaphenylbenzene can be taken as a promising building block for designing porous polymers with special properties.