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Chemical derivatization of the substrate is not widely used in the preparation of the modern commercially available anion-exchangers for suppressed IC, since it usually provides very limited selectivity, and such stationary phases can be used for separating only 5-9 anions. In the current work for the first time the novel ways for obtaining hyperbranched anion-exchangers with improved selectivity toward inorganic anions and organic acids based on chemically derivatized polystyrene-divinylbenzene (PS-DVB) substrate are proposed. In the first approach the hyperbranched ion-exchange layers are formed on the surface of aminated substrate via step by step modification with diepoxides and primary amines containing various charged and polar substitutes. The structure and the charge of the substitute in primary amine, as well as the location of the particular amine in the functional layer considerably influences selectivity, especially for separating weakly retained anions, which is demonstrated in the present work. The second approach includes the use of polyamines with primary, secondary and/or tertiary amino groups in the hyperbranched ion-exchange layers with different branching degree. In this case considerable selectivity variations are provided by choosing polyamine structure, the way of its attachment, and appropriate crosslinking or hydrophilizing reagents for quternization of its amino groups. Anion-exchangers obtained in the present work provide the separation of up to 23 anions in one run even with 100 × 4 mm i.d. columns, including standard inorganic anions, oxyhalides, mono-, di-, and tri-valent organic acids and some strongly retained polarizable anions. Some of the obtained stationary phases provide baseline separation of such weakly retained organic acids as glycolic, lactic, acetic, and formic, which nowadays can’t be resolved to baseline with the existing commercially available columns for suppressed IC. The application of the novel anion-exchangers for the analysis of beverages (apple and orange juices, beer, tea, etc.), pharmaceutical preparations, and environmental samples is demonstrated.