We have designed and synthesized a family of dinuclear cyanido-bridged complexes [PY5Me₂Ru(μ-CN)Ru(dppe)CpMe_n][PF₆]₂ (PY5Me₂ = 2,6-bis (1,1-bis (2-pyridyl)ethyl) pyridine, Cp = cyclopentadienyl, n = 0, 2[PF6]₂; n = 1, 3[PF6]₂; n = 5, 4[PF6]₂) by using a mononuclear complex [PY5Me₂Ru(μ-CN)][PF₆] (1) as the precursor. All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis. The one-electron oxidation complexes 2³⁺, 3³⁺ and 4³⁺ obtained in situ all show a MMCT absorption band in the visible range. The MMCT energy increases as the redox potential of the N-terminal fragments decreases, and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases, supported by the TDF/TDDFT calculations.