This study reports the syntheses of four polymeric sorbents based on nucleophilic substitution of Poly(4-vinylbenzylchloride/ethylene glycol dimethacrylate). Polymerization was executed by a simple thermal initiated bulk polymerization procedure. Ground polymer particles were functionalized through reaction with the nucleophiles triethylamine, imidazole, piperidine and pyrrolidine. Mixed-mode phases were characterized by infrared spectroscopy, nitrogen sorption porosimetry and potentiometric titration for determination of chloride content. Furthermore, materials were tested and evaluated for enrichment of seven pharmaceutical and endocrine -disrupting compounds at low ng mL(-1) levels. Results demonstrate that the imidazole modified sorbent led to high and constant recovery rates for nearly all tested compounds. Therefore, this polymer was further tested for applicability with two environmental samples. Spiked tap and river water showed similar results as in evaluation experiments. Moreover, the developed method was validated regarding linearity, repeatability, instrumental limits and stability of analytes according to international guidelines.