The metal cation binding ability of cone-p-tert-butylhexahomotrioxacalix[3]arene tris(acetic acid) was investigated by ¹H NMR and complementary semi-empirical calculations. NMR showed significant shifts with Na⁺, K⁺, Ag⁺ and, to a lesser extent, Pb²⁺. The macrocyclic protons undergoing the greatest shifts imply that these cations bind inside the cavity composed of the phenoxy and carbonyl oxygen atoms. Metal complexes were modelled using a semi-empirical approach and, in general, their geometry optimised structures were in agreement with NMR data. U-tube transport experiments demonstrated that the macrocycle actively transported Cr³⁺, Fe³⁺, Co²⁺ and Cu²⁺ through the organic phase.