Reaction of [Cu(pda)(Phen)2] ·6H2O and [Cu(oda)(Phen)2] ·8H2O {pdaH2 =pentanedioic acid; odaH2 =octanedioic acid; Phen =I, 10-phenanthroline} with ethanolic solutions of sodium perchlorate gives the two binuclear copper(Il) perchlorate salts [Cuz(pda)(Phen)4](ClO4 )25H2O·C2H5OH (1) and [Cu2(oda)(Phen)4](CIO4 )2·2.76H2O·C2H5OH (2), respectively. The X-ray crystal structures of 1 and 2 are quite similar with each comprising a discrete [Cu2(dicarboxylate)(Phen)4]2+ dication, two uncoordinated perchlorate anions, an uncoordinated ethanol and several uncoordinated water molecules. The copper centres have N4O ligation with each metal having approximately square pyramidal geometry. {[Cu(pda)JL reacts with ammonium hydroxide to form the polymeric copper(Il) amine species {[Cu2(pda)2(NH3 )4(H2O)2 ]·4H2OL (3). The structure of 3, as determined by X-ray crystallography, consists of polymeric chains in which the bridging pda2 anions link two crystallographically similar copper atoms. The copper atoms are also ligated by two transoidal ammonia nitrogens and an oxygen atom from an apical water molecule, giving the metals an overall N2O3 , slightly distorted, square pyramidal geometry. Spectroscopic and magnetic data for the three complexes are also reported.