Removal of cationic pollutants, including dyes, herbicides, and antibiotics from water is significant owing to their persistence, bioaccumulation, carcinogenicity, mutagenicity, and reproductive risks. In this paper, a calixarene-tetraphenyl ethylene containing copolymer adsorbent, named CP-TPE, was synthesized using the Suzuki-Miyaura coupling reaction between the resorcinol calixarene and tetraphenyl ethylene boric acid esters. Subsequently, the phenolic groups on the CP-TPE were further reacted with chlorosulfonic acid, resulting in a sulfonated product named CP-TPE-SO3H. The introduction of the sulfonate groups not only significantly improved the hydrophilicity of CP-TPE-SO3H but also enhanced the electrostatic interaction between CP-TPE-SO3H and cationic molecules, achieving an outstanding maximum adsorption capacity for paraquat (representative herbicide, 300.06 mg g−1) and tetracycline hydrochloride (representative antibiotic, 888.74 mg g−1), which surpassed the majority of reported polymeric adsorbents. Moreover, the k2 of CP-TPE-SO3H on TC (0.0407 g mg−1 min−1) reached the maximum value reported so far. This study demonstrated the significance and superiority of sulfonation modification in synthesizing POPs-based adsorbents, which can be potentially employed in real wastewater treatment.