The synthesis and spectroscopic studies of a dicopper(II) double helicate capable of binding anions is described. X-Ray crystallographic analysis of three anion variations of the complex have shown that the helicate is capable of accommodating anions with an approximate volume of 0.09 nm(3) and smaller. ESI-MS revealed that the supramolecular complexes retain the 2 : 2 ligand : metal cluster in solution. Spectrometric analysis has shown the complex is capable of binding anions in a 1 : 1 ratio of helicate to anion, in the order SO42- > HPO42- > ClO4- similar to BF4- similar to NO3-. We demonstrate that coordination to the metal centre, H-bonding and electrostatic interactions all play a role in encapsulating the anions.