Ruthenium(II) complexes containing both Ru–C bonds and azopyridine-based supporting ligands were synthesized by substituting chlorido ligand(s) in the complex with CO or CN^–. Although only the cis-isomer of [Ru(pap)₂(CO)Cl]⁺ (pap = 2-(phenylazo)pyridine) formed, the trans-isomer of [Ru(pap)₂(CN)₂] formed preferentially despite the use of a cis- precursor. The new ruthenium complex cis-[Ru(pap)₂(CO)Cl]⁺ was characterized by various methods including NMR and IR spectroscopy. The molecular structures of cis-[Ru(pap)₂(CO)Cl]⁺ and trans-[Ru(pap)₂(CN)₂] were determined by X-ray structure analysis. The ligand-centered redox properties and characteristic charge transfer absorptions of these complexes were studied using electrochemical and spectroscopic techniques. The obtained experimental data is compared with that from analogous poly-pyridyl-containing ruthenium(II) complexes.