Six rhenium(I) κ3N-dicarbonyl complexes with 4′-(4-substituted phenyl)terpyridine ligands were evaluated in their ground and excited states. These complexes, bearing substituents of different electron-donating strengths—from CN to NMe2—were studied by a combination of transient IR (TRIR), electrochemistry, and IR spectroelectrochemistry, as well as time-dependent density functional theory (TD-DFT). They exhibit panchromatic absorption and can act as stronger photoreductants than their tricarbonyl counterparts. The ground- and excited-state potentials, absorption maxima, and lifetimes (250–750 ps) of these complexes correlate well with the Hammett σp substituent constants, showing the systematic effect of remote substitution in the ligand framework. TRIR spectroscopy allowed us to assign the lowest singlet and triplet excited states to a metal-to-ligand charge-transfer (MLCT) character. This result contrasts our previous report on analogous κ2N-tricarbonyl complexes, where remote substitution switched the character from MLCT to intraligand charge transfer. With the help of TD-DFT calculations, we dissect the geometric and electronic effects of coordination of the third pyridine, local symmetries, and increasing conjugation length. These results give valuable insights for the design of complexes with long-lived triplet excited states and enhanced absorption throughout the visible spectrum, while showcasing the boundaries of the excited-state switching strategy via remote substitution.