Two new copper complexes [Cu(Hdpa)2(en)] (1) and [{Cu2(μ-na)4(CH3OH)2}·2CH3OH] (2) (where en is ethylene diamine, Hdpa is 2′-carboxy-[1,10-biphenyl]-2-carboxylate anion and na is 1-naphtalenecarboxylate) have been synthesized and their crystal structures were determined by X-ray crystallography. Complex 1 was prepared from the reaction of Cu(NO3)2·3H2O with ethylene diamine and 2,2′-biphenyldicarboxylic acid in a mixture of water and methanol and complex 2 was prepared from the reaction of CuSO4·5H2O with 1-naphtalenecarboxylic acid in methanol. The two complexes were characterized by IR, UV–vis, luminescence and elemental analysis. Moreover, complex 2 was characterized by EPR spectroscopy and thermogravimetric analysis. Complex 1 is a monomer and complex 2 is a dimer with a paddle-wheel structure; both structures are without precedent in the literature. 0 BOOKMARKS