The present work shows the pivotal role of N-donor substituents attached to 1,10-phenanthroline at the 4,7-positions in perturbation of ground- and excited-state properties of fac-[ReCl(CO)3(R2phen)]. Excited-state processes occurring upon photoexcitation in the designed systems were thoroughly explored with a wide range of steady-state and time-resolved spectroscopic techniques, including transient absorption, as well as experimental results were complemented by theoretical studies based on the density functional theory (DFT). It was demonstrated that the attachment of six-membered heterocyclic amines (piperidine─ppr, morpholine─mor, and thiomorpholine─tmor) is a very effective tool for extending absorptivity and excited-state lifetimes of resulting fac-[ReCl(CO)3(R2phen)] due to the contribution of the excited state localized on the phenanthroline-based ligand. Both absorption and emission properties of these systems were attributed to configurationally mixed MLCT/IL excited states. Re(I) complexes with phenoxazine (pxz) and phenothiazine (ptz) substituents were shown to possess charge-separated excited states, clearly evidenced by the simultaneous presence of signals typical of phen-* and pxz+* or ptz+* in transient absorption spectra. Both complexes are rare examples of NIR light-emitting coordination compounds. The decoration of the phen framework with less polar 9,9-dimethyl-9,10-dihydroacridine (dmac) groups resulted in the formation of [ReCl(CO)3(R2phen)] with mixed 3MLCT/3ILCT triplet excited state.