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 m2 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.