Several copper(II) complexes containing new tripodal polyimidazole ligands have been synthesized and characterized by X-ray crystallography, UV-vis and EPR spectroscopies, and cyclic voltammetry. The tripodal polyimidazole ligands have been prepared in good yields and characterized by IH and 13C NMR and mass spectrometry. X-ray crystallographic parameters for the copper(II) compounds are as follows : compound 8, C15H21N7PClF6Cu, 543.34 g/mol, monoclinic space group (P2(1)/c), a = 16.585(3) angstrom, b = 12.570(3) angstrom, c = 10.540(3) angstrom, beta = 105.34(2)degrees, V = 2118.8 angstrom3, Z = 4, 3042 independent reflections with I > 3sigmaAbsolute value of I to a maximum 2theta scan of 50-degrees, R = 0.040, R(w) = 0.039; compound 9, C15H21N7PClF6Cu, 543.34 g/mol, orthorhombic space group (Pbca), a = 16.487(5) angstrom, b = 16.246(5) angstrom, c = 16.555(5) angstrom, V = 4434.1 angstrom3, Z = 8, 2240 independent reflections with I > 3sigmaAbsolute value of I to a maximum 2theta scan of 50-degrees, R = 0.075, and R(w) = 0.057. Both compounds have distorted trigonal bipyramidal structures. Three imidazole nitrogen atoms of each tripod occupy equatorial positions of the trigonal bipyramid, while the amine nitrogen atom and chlorine atom occupy apical sites. In both complexes the imidazole pendants are twisted from the chelate planes with torsion angles ranging from 6.7 to 22-degrees. The Cu-N(amine) bond length in compound 8 is 0.023 angstrom longer than the Cu-N(amine) bond length in compound 9. The EPR spectral data for both compounds are consistent with the retention of the solid-state structure in frozen DMF/MeOH (1:1) solution. The UV-vis spectrum of compound 8 is red-shifted relative to compound 9, indicating that the corresponding tripod ligand in 8 is a weaker field ligand. Both compounds display quasireversible one-electron redox behavior in acetonitrile. The E1/2 values for compound 8 and 9 are -0.193 and -0.225 V vs Ag/AgCl, respectively. The redox potentials of 8 and 9 are shifed cathodically compared to a related copper(II) complex, [Cu(TMIMA)Cl]+ (TMIMA = tris((1-methylimidazol-2-yl)methyl)amine), which contain only 2-substituted 1-methylimidazole pendants.