Synthesis of covalently linked porous polymers with high surface area and larger pore volume for two or more task‐specific functionalities is always a big challenge. In this article, the facile Friedel–Crafts reaction is employed to construct the hierarchical hybrid porous polymers (HPPs) from tetraphenyladamantane and octavinylsilsesquioxane. The resulting polymers, HPP‐1 to HPP‐3, possessed the surface areas from 1356 to 1511 m2 g−1, and the pore volumes from 2.05 to 2.67 cm3 g−1. All these polymers feature micropores, mesopores, and macropores in nature. The resultant polymers exhibit high CO2 adsorption capacity up to 2.0 mmol g−1 (8.82 wt %), at 273 K, 1.0 bar, and the maximum Rhodamine B (RB) sorption capacity of 653.6 mg g−1. To illustrate the adsorption process, the effects of factors, contact time, initial concentration, temperature, and pH value on the adsorption capacity of RB were studied. The adsorption equilibrium data displayed a better fitting to the Langmuir isotherm model than the Freundlich model and the adsorption kinetics fitted well with the pseudo‐second‐order kinetic model. The recycle experiments displayed that the capacity recovery was still higher than 95% after four cycles. Theses polymers are promising to be the adsorbents for capturing CO2 and removing RB. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 136, 48572.