The copper(II) complex [Cu(bdoa)(H2O)2] (1; bdoaH2 = benzene-1,2-dioxyacetic acid) reacts with aniline in an ethanol-water mixture to give [Cu(bdoa) (C6H5NH2)2]2C6H5NH2 (2). The X-ray crystal structure of 2 shows the asymmetric unit to contain two mononuclear [Cu(bdoa)(C6H5NH2)2] units and a solvate aniline molecule. Each copper(II) atom has essentially square planar coordination and is bonded to the nitrogen atoms of two trans aniline molecules and a single oxygen atom from each of the two carboxylate moieties of the bdoa2− ligand. The ether oxygen atoms of the bdoa2− bond only weakly to the metal, and one of the metals also interacts weakly with the solvate aniline. Compound 1 reacts with 2,2′-bipyridine (bipy) to form the binuclear copper(II) complex [Cu2(bdoa)(bipy)4]bdoa·8.66H2O (3). The X-ray crystal structure of 3 shows a discrete [Cu2(bdoa)(bipy)4]2+ dication, an uncomplexed bdoa2− dianion and water molecules linked by OH…O hydrogen bonding. The dication has two-fold crystallographic symmetry, and the coordination of the unique copper atom is N4O2 distorted octahedral. Only one of the carboxylate oxygens is strongly bonded and the other forms a weak interaction with the metal. Spectral, magnetic, conductivity, voltammetry and thermogravimetric data for the complexes are given.