In this study, a new cation-exchange coating for stir bar sorptive extraction (SBSE) based on poly (acrylic acid-ethylene dimethacrylate) monolithic material was synthesized. The effect of polymerization conditions such as the ratio of functional monomer to cross-linker and the content of porogenic solvent on the extraction efficiencies were investigated in detail. The monolithic material was characterized by elemental analysis, scanning electron microscopy and infrared spectroscopy. In order to evaluate the usability of the new coating for the extraction of inorganic cations, the analysis of soluble K+, Mg2+and Ca2+in milk by ion chromatography with conductivity detection was selected as a paradigm. Several extractive parameters, including pH value in sample matrix, desorption solvent, extraction and desorption time were optimized. Under the optimum conditions, low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target cations were achieved within the range of 0.12–0.28 and 0.4–0.92 μg L−1, respectively. The method also showed good linearity, simplicity, practicality and low cost for the extraction of inorganic cations. Finally, the proposed method was successfully used to analyse three different trademarks of commercial milk samples with satisfactory recoveries in the range of 71.1% to 102.8%. [ABSTRACT FROM AUTHOR]