The synthesis and characterization of two coordination polymers, {Cu[Mo-V(bdt)(3)]center dot 0.5Et(2)O)(n) (1.0.5Et(2)O, bdt: o-benzenedithiolato) and {Ag-I[Mo-V(bdt)(3)]}(n) (2), composed of redox-active [Mo-V(bdt)(3)](-) metalloligand with Cu-I and Ag-I ions are reported. The complexation reactions of [Mo-V(bdt)(3)](-) with Cu-II(ClO4)(2) or (AgClO4)-Cl-I commonly lead to the formation of one-dimensional (1-D) coordination polymers. The presence of Cu-I in 1.0.5Et(2)O strongly indicates that the Cu-II ion is reduced during the complexation reaction with [Mo-V(bdt)(3)](-), which acts as an electron donor. The total dimensionalities of the assembled structures of 1.0.5Et(2)O and 2 are significantly different and related to the type of additional metal ions, Cu-I and Ag-I In contrast to the isolated 1-D chain structure of 1.0.5Et(2)O, complex 2 has a three-dimensional (3-D) assembled structure constructed from additional pi-pi stacking interactions between adjacent [Mo-V(bdt)(3)](-) moieties. These structural differences influence the solubility of the complexes in organic solvents; complex 1.0.5Et(2)O is soluble as origomeric species in highly polar solvents, while 2 is insoluble in organic solvents and water. Coordination polymers 1.0.5Et(2)O and 2 were investigated by UV-vis spectroscopy in the solid state, and that in solution together with their electrochemical properties were also investigated for 1 because of its higher solubility in polar organic solvents. Complex 1 0.5Et(2)O dissolved in CH3CN demonstrates concentration-dependent UV-vis spectra supporting the presence of coordinative interactions between [Mo-V3(bdt)(3)](-) moieties and Cu-I ions to create the origomeric species even in solutions, an observation that is supported also by electrochemical experiments.