Metal alkoxides [Cr(III), Mg(II), Mo(V), V(III), and W(V)] taken in 1:1 equimolar proportions, calculated per one D-glucose unit, reacted with a pregelatinized starch in microwave assisted processes into the corresponding starch cationic metal derivatives. In each case, the crosslinking occurred as a consequence of the substitution of two alkoxide groups in the metal alkoxide reagents with two D-glucose units. Involvement of the 6-CH2OH moiety of the D-glucose units in formation of the valence bond with the metal cation was the most likely, but the metal cation was additionally coordinated to the other hydroxyl groups of the D-glucose units. Chromium(III) and vanadium(II) complexes hydrolysed in full by their contact with water, whereas the other metal complexes hydrolysed only in part.