Preparation of magnesium, lanthanum, and bismuth(III) complexes of 3.6 kDa maltodextrin and some properties of the resulting materials are presented. The metal derivatives contain metals bound to the oxygen atoms of the hydroxyl groups of maltodextrin. Additionally, the metal atoms are coordinated to the hydroxyl groups of the D-glucose units of the macroligand. Such coordination stabilized the metal - oxygen bond against hydrolysis, even in boiling water. The presence of magnesium and lanthanum atoms increased the thermal stability of maltodextrin, whereas bismuth atoms decreased it.