2-4, 3-4, 2-8, 3-8, 3-6, 4-6, 6-8, 6-10-ionenes (polymers with quaternary nitrogen atoms in the main chain) served as modifiers in synthesizing polyelectrolyte sorbents for ion chromatography. The approaches to the synthesis and their stability are discussed. Cluster analysis was applied to separate aliphatic ionenes to three groups as chromatographic modifiers, namely hydrophilic, hydrophobic, and intermediate. Each group is characterized by a certain selectivity to sulfate, perchlorate, iodide and thiocyanate. The sorbents show high selectivity and efficiency up to 15,000 theoretical plates per meter.