Summary It was shown that potato starch formed Werner‐type complexes. In these complexes a metal atom is ligated by the lone electron pairs of hydroxyl groups from d ‐glucose units and phosphate groups in starch. Acetate, chloride and nitrate were counter‐ions to the transition metal atoms. The metal cations bound preferentially to the phosphoric acid moiety of amylopectin, but secondarily they were co‐ordinated by the hydroxyl groups of the d ‐glucose units. This resulted in the formation of clathrate cages in which a significant number of the water molecules were trapped. Such structures were able to co‐ordinate further metal cations. Only Mn(II) and Co(II) ions, with acetate counter‐ions, neither formed clathrate cages nor were co‐ordinated by the hydroxyl groups of the d ‐glucose of starch.