A series of the most common chelators used in magnetic resonance imaging (MRI) and in radiopharmaceuticals for medical diagnosis and tumour therapy, H4dota, H4teta, H8dotp and H8tetp, is examined from a chemical point of view. Differences between 12- and 14-membered tetraazamacrocyclic derivatives with methylcarboxylate and methylphosphonate pendant arms and their chelates with divalent first-series transition metal and trivalent lanthanide ions are discussed on the basis of their thermodynamic stability constants, X-ray structures and theoretical studies.