A process for preparing cyclooctaamylose by enzymatic cleavage of an aqueous preparation of starch in the presence of a complexing agent is disclosed. As a selective complexing agent for cyclooctaamylose, a compound of the formula I is employed. ##STR1## in which A, B, D and E, independently of one another, represent ##STR2## (R=hydrogen, alkyl, hydroxyl, alkoxy or carboxyl radical), and m, n, o and p are within the limits 0 to 20, with the proviso that the number of atoms forming the ring is within the limits from 13 to 24. The compounds prepared by the process of the invention are useful in the medicaments sector, in crop protection and cosmetics, or in the foodstuffs industry.