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Molecular photosensitizers that are able to store multiple reducing equivalents are of great interest in the field of solar fuel production, where most reactions involve multielectronic reduction processes. In order to increase the reducing power of a ruthenium tris‐diimine charge‐photoaccumulating complex, two structural modifications on its fused dipyridophenazine‐pyridoquinolinone ligand were computationally investigated. Addition of an electron‐donating oxime group was calculated to substantially decrease the reduction potentials of the complex, thus guiding the synthesis of a pyridoquinolinone‐oxime derivative. Its spectroscopic and (spectro)electrochemical characterization experimentally confirmed the DFT predictions, with the first and second reduction processes cathodically shifted by −0.24 and −0.14 V, respectively, compared to the parent complex. Moreover, the ability of this novel artificial photosynthetic system to store two photogenerated electrons at a more reducing potential, via a proton‐coupled electron‐transfer mechanism, was demonstrated. [ABSTRACT FROM AUTHOR]