This study reports that polynuclear charge-transfer complexes consisting of Ce³⁺ and a Lindqvist-type polyoxometalate center, either W₆O₁₉²⁻ or Mo₆O₁₉²⁻, function as an all-inorganic visible-light-absorbing chromophore. The polynuclear W₆O₁₉/Ce and Mo₆O₁₉/Ce complexes showed an intense absorption band from the UV region to 520 and 600 nm, respectively. The FTIR and Ce L_III-edge X-ray absorption measurements confirmed that the visible absorption is due to the oxo-bridged W⁶⁺/Ce³⁺ and Mo⁶⁺/Ce³⁺. As polyoxometalates have efficient redox and catalytic properties, their visible-light sensitization could provide a new building block for fabricating inorganic, molecular-based photosynthetic assemblies.