Cationic surface-active monomers with 11-acryloyloxyundecyl tail in quaternary ammonium group and the corresponding comb-like polyelectrolytes are investigated. The sources of quaternary ammonium were aliphatic amines (trimethylamine and triethylamine) or aromatic and aliphatic cyclic amines (N-methylpiperidine, N-methylmorpholine, pyridine, quinoline). The monomer to polymer transformation increases the solubilization capacity of surfactant in one order of magnitude. The comb-like polyelectrolytes are capable to effective solubilization of hydrophobic probe over the wide concentration range including extremely low concentrations of the polymer. There aren't any precipitations of comb-like polyelectrolytes with temperature decrease unlike of many ionic low-molecular weight surfactants. Solubilization capacity of the hydrophobic probe by comb-like polyelectrolyte is slightly influenced by the molecular weight of the polymer and is determined by the nature of the ionic group of comb-like polyelectrolyte and counterion.