LC on short monolithic columns (Convective Interaction Medium Disks) was applied to investigate several specially synthesized water soluble polycations of different charge type (primary, tertiary, quaternary amine), as well as a copolymer of neutral saccharide and cationic monomers, regarding their ability to form reversible complexes with DNA. For this purpose, two separation modes were used, namely, pseudo-affinity and cation-exchange chromatography. Synthetic polynucleotides, namely, polyriboadenylic acid (poly(rA)) and polyribocytidylic acid (poly(rC)), were used as approximate structural analogues of DNA. In first case, the hypothetical specific binding between dissolved polymers and polynucleotide (poly(rA) or poly(rC)), covalently attached to epoxy-bearing monolithic sorbent, has been studied and compared to the results obtained using cation exchange chromatography. Quantitative parameters of interactions between macromolecules were established using frontal elution method.