A supramolecular complex between an ionic monomer 3-sulfopropyl methacrylate (SPMAK) and crown ether 18-crown-6 (18C6) has been employed to prepare a strong anionic cylindrical polyelectrolyte brush poly(potassium 3-sulfopropyl methacrylate) (PSPMAK) by atom transfer radical polymerization (ATRP) in polar solvent dimethyl sulfoxide (DMSO). This strategy solved the problem of the solubilities of the incompatible hydrophobic poly-initiator and hydrophilic ionic monomer. The formation of the PSPMAK brush is well proven by H-1 NMR, aqueous gel permeation chromatography (GPC), dynamic light scattering (DLS), static light scattering (SLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Cleavage of the side chains and further analysis reveal that the initiating efficiency of the polymerization is as low as 0.35.