The application of neutral dicopper helicates to the encapsulation of a number of anions was investigated. Two dicopper salen derived helicates were studied which contained phenolic and either iminophenyl (1) or oxime (2) donor groups. UV-visible spectroscopy was used to determine the binding stoichiometry and formation constants of the anion complexes. Complex binding was supported by electrospray ionisation mass spectrometry. Receptor 1 possessed a remarkable selectivity for sulfate in isopropanol (IPA) for which a log K value of 5.07 ± 0.24 was obtained. Receptor 2 bound all anions studied more strongly than 1. Crystal structural data supports the proposition that there is a steric barrier to contraction of 1 from the bulky iminophenyl groups. Receptor 2 was not restricted by the small oxime moieties allowing for optimum copper-anion interactions.