Polymeric copper(II), [Cu(mu-dpc)(mu-4-hymp)] (n) (1), and monomeric nickel(II), [Ni(dpc)(4-hymp)(H(2)O)(2)]center dot H(2)O (2), (dpc: dipicolinate, 4-hymp: 4-hydroxymethyl pyridine), dipicolinate complexes have been prepared and characterized by spectroscopic (IR, UV-Vis, EPR), thermal (TG/DTA), X-ray diffraction technique and electrochemical methods. In both the dipicolinate complexes, the dpc dianion acts as a tridentate ligand. In polymeric copper(II) complex, the 4-hymp and dpc ligands adopt a bridging position between the Cu(II) centers, forming the elongated octahedral geometry. The polymeric chains are linked to one another via O-H center dot center dot center dot O hydrogen bond interactions, forming the 3-D polymeric structure. The Ni(II) ion is bonded to dpc ligand through pyridine N atom together with one O atom of each carboxylate group, two aqua ligands and N pyridine atom of 4-hymp, forming the distorted octahedral geometry. The Ni(II) complexes are connected to one another via O-H center dot center dot center dot O hydrogen bonds, forming R (4) (2) (18) motifs in 2-D pattern. The powder EPR spectra of copper(II) complex have indicated that the paramagnetic center is in rhombic symmetry with the Cu(2+) ion having distorted octahedral geometry. IR and UV-Vis spectroscopes all agree with the observed crystal structure.