Complexes of the (H2Im)4[CuF6], (H2Im)2[CuF4(H2O)2] type (H2Im=imidazolium cation) and Cu(HIm)4X2 (X = Cl or Br; HIm=imidazole) have been prepared in aqueous solution by the interaction of CuO·nH2O with the respective halide in the presence of imidazole. Formation of a particular complex species has been shown to be dependent on the reaction solution pH and also on the nature of the halide. The complexes were characterised on the basis of FT-i.r., u.v.–vis. and e.s.r. spectroscopy and by measurement of magnetic susceptibilities and solution electrical conductivities. Cyclic voltammetry revealed a two-peak quasi-reversible response for [Cu(HIm)4Br2], while other complexes produced overall irreversible voltammographs. Thermal decomposition profiles are consistent with the proposed formulations.