Metal ions and polyvalent organic cations take part in many processes proceeding in living organisms. These processes are associated with the formation of coordination compounds and molecular complexes. An important group of bioligands is made up of biogenic amines, which occur in practically all forms of organisms and their reactions with nucleic acids play an essential role in processes of genetic information transfer. Metals present in cells should be considered as interfering agents, which change the character of interactions. Reactions, including the formation of molecular complexes and metallation of a number of polyamines, have been described. The effectiveness of non-covalent interactions of amines, besides charge, is determined by structural factors (this fact elucidates reaction specificity) and these interactions are of an ion–ion, ion–dipole type, both in binary and ternary systems, that include fragments of nucleic acids (nucleosides, nucleotides) and metal ions, as well. Differences in the character of the interactions can elucidate different biological activity of biogenic amines compared to their analogues, not occurring in living organisms.Principal metallation sites of discussed bioligands in ternary sysytems, including fragments of nucleic acids, are amino groups of polyamines and endocyclic nitrogen atoms N(1), N(7) and N(3) of purine and pyrimidine rings of nucleosides as well as phosphate groups of nucleotides, respectively.