AbstractMaterials based on the cationic copper(II) hexanuclear 18‐membered metallacrown [18‐MC ‐6]6+ (2phH=2‐piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single‐crystal X‐ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen‐bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO4− (M=Tc, Re). The MO4− trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water.