We successfully prepared two different classes of hypercrosslinked porous organic polymers (HPPs)—the tetraphenylethene (TPE) and (4-(5,6-Diphenyl-1H-Benzimidazol-2-yl)-triphenylamine (DPT) HPPs—through the Friedel−Crafts polymerization of tetraphenylethene and 4-(5,6-diphenyl-1H-benzimidazol-2-yl)-triphenylamine, respectively, with 1,4-bis(chloromethyl)benzene (Ph-2Cl) in the presence of anhydrous FeCl3 as a catalyst. Our porous materials exhibited high BET surface areas (up to 1000 m2 g−1) and good thermal stabilities. According to electrochemical and dyes adsorption applications, the as-prepared DPT-HPP exhibited a high specific capacitance of 110 F g−1 at a current density of 0.5 A g−1, with an excellent cycling stability of over 2000 times at 10 A g−1. In addition, DPT-HPP showed a high adsorption capacity up to 256.40 mg g−1 for the removal of RhB dye from water.