Three new perylene diimide (PDI)-based ligands have been synthesized by the covalent attachment of dipyrido[a,c]phenazine moiety to one of the bay-positions of PDI, while the second position has been substituted with either a 4-tert-butylphenoxy or a pyrrolidinyl group to obtain two types of chromophores, Ph-PDI and Py-PDI, respectively, with distinct properties. In the case of Py-PDI, the resultant 1,7- and 1,6-regioisomers have been successfully separated by column chromatography and characterized by (1)H NMR spectroscopy. The ligands have been employed to prepare donor-acceptor-based ensembles incorporating the covalently linked PDI and Ru(II) polypyridine complex as the acting chromophores. A comprehensive study of the excited-state photodynamics of the ensembles has been performed by means of electrochemical and steady state and time-resolved spectroscopic methods. Although, in all the three ensembles, the photoexcitation of either chromophore resulted in a long-lived triplet excited state of PDI ((3)PDI) as the final excited state, the photochemical reactions leading to the triplet states were found to be essentially different for the two types of the ensembles. In the case of the Ph-PDI-based ensemble, the excitation of either chromophore leads to the electron transfer from the Ru(II) complex to Ph-PDI, whereas for the Py-PDI-based ensembles, the electron transfer is observed in the opposite direction and only when the Ru(II) complex is excited. The difference in the behavior was rationalized based on electrochemical study of the compounds, which has shown that the Ph-PDI chromophore is a better electron acceptor and the Py-PDI chromophores are relatively better electron donors. This study shows a chemical approach to control the photoreactions in PDI-based dichromophoric ensembles including the possibility to switch the direction of the photoinduced electron transfer.