(2R,4R,6R,8R)-1,9-Dihydroxy-3,5,7-trioxanonane-2,4,6,8-tetracarboxylic acid (H4TT) has been prepared via a catalytic oxidation of D-trehalose with molecular oxygen and via a two-step oxidation with periodate and chlorite. The lanthanide complexes have 1:1 and 1:2 metal-ligand stoichiometries. Ln(III)-induced effects on chemical shifts, relaxation rates, and vicinal proton-proton coupling constants yielded information on the geometries of these complexes. The complexes with Ln(TT) stoichiometry have 2 water molecules in the first coordination sphere of Ln(III), and the remaining 6-7 positions are occupied by carboxylate, ether, and -CH2OH oxygens of the two oxidized sugar units of TT. The -CH2OH oxygens are coordinated for about 85% of the time. The Ln(TT)(2) complexes have one TT ligand that is bound in a hexadentate fashion via the two terminal oxydiacetate units (each in a tridentate fashion), whereas the second TT ligand has only one oxydiacetate unit coordinated. The exchange between bound and free oxydiacetate moieties in Ln(TT)(2) is rapid on the NMR time scale. in about 20% of the TT ligands of this complex one of the coordinated carboxylate groups is substituted by a -CH2OH group.