An approach for fabrication of core-shell composite beads was described, with polystyrene-divinylbenzene (PS-DVB) as the core and multi-walled carbon nanotubes (MWCNTs) as the shell through electrostatic attraction-induced self-assembly. MWCNTs were easily quaternized with defined number of bonded layers and desirable positive charge by a multi-step synthesis, using methylamine and 1,4-butanediol diglycidyl ether as monomers to build a branching polymer that has quaternary ammonium groups. PS-DVB beads were sulfonated by sulfuric acid to provide opposite charge, which had electrostatic interaction with quaternized MWCNTs. Functionalization of MWCNTs was characterized by techniques like Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TGA) and scanning electron microscopy (SEM).The dispersion of MWCNTs in deionized water was enhanced after the grafting of cationic polyelectrolytes on them, which was in agreement with the positive charge at any pH value. The results obtained by FTIR and SEM confirmed the formation of ionic bondings between the sulfonated PS-DVB particles and quaternized MWCNTs. A 100 × 4.0 mm i.d. column was packed with the PS-DVB/MWCNT composite beads, with a capacity of 56 µeq/column. Separation of inorganic anions, such as F^-, Cl^-, NO₂^-, Br^-, NO₃^-, SO₄^2- and PO₄^3- were performed with good resolution and high column efficiency. The stationary phase was rigid, chemically stable and showed good ion-exchange characteristics.