The binding properties, in aqueous solution, toward lithium ion of aza- and azaoxo- macrocycles with cage and cylindrical molecular topology are reviewed. The synthetic procedures and the acid-basic behavior are reported. Most of these compounds are able to selectively encapsulate the small lithium ion in aqueous solution. NMR spectroscopy, mainly 1 3 C and 7 Li, has been used to study the encapsulation equilibria. Few crystal structures of lithium complexes, indicating the lithium ion encapsulation have been reported.