Via an oxidation reaction of Cu(I) iodide with pyridine-2,6-dicarboxylic acid (H2L) in DMF three copper(II) complexes, [(CH3)(2)NH2](2)[CuL2] (1), K-2 [CuL2]center dot H2L center dot H2O(2) and [Cu(L)(H2O)](n) (3), were synthesized and characterized. The structures of 1-3 were determined by single crystal X-ray diffraction studies. In-situ DMF decomposition produces dimethylamine base under solvothermal conditions and a proton transfer reaction takes place for the complex formation of 1. 3-D networks are stabilized in 1 and 2 via hydrogen bonds. Complex 3 is a 1-D coordination polymer with Cu-O semi-coordination bonds. Thermal decomposition of the complexes results in the corresponding metal oxides. Also, the electrochemical behavior of 1 was determined to be a metal-centered and diffusion-controlled, one-electron reduction process.