Chemistry and biological activities of macrocyclic polyamines have been studied to disclose (1) special features of mode of their proton uptake ; (2) uptake of biological polyanions (such as TCA cycle polycarboxylates, phosphate, ATP and carbonate) and of catechols (such as dopa and dopamine) ; (3) inclusion of soft metal ions (e.g. Cu2+) ; (4) selective uptake of hard metal ions (e.g. Mg2+) ; (5) peptide-like functions to stabilize unusual oxidation state of metal ions (e.g. Cu3+, Ni3+) ; (6) superoxide dismutase-like activities by macrocyclic polyamine complexes ; (7) biogenic polyamine-like activities ; and (8) heme-like O2-uptake and activation functions by metal complexes. These newly discovered properties will prove to be useful for the future development of entirely new type of medicines, chemicals, catalysts and so on.