To bind or not to bind: Driven by the motivation to increase the (photo)stability of traditional Cu(I) photosensitizers, multidentate diimine ligands, which contain two additional donor sites, were designed. To this end, a systematic series of four 1,10-phenanthroline ligands with either OR or SR (R = Pr-i or Ph) donor groups at the 2 and 9 positions and their resulting hetero- and homoleptic Cu(I) complexes were prepared. In addition, the related Ru(II) complexes were also synthesized to study the effect of another metal center. In the following, a combination of NMR spectroscopy and X-ray analysis was used to evaluate the impact of the additional donor moieties on the coordination behavior. Most remarkably, for the homoleptic bis(diimine)copper(I) complexes, a pentacoordinated copper center, corresponding to a (4 + 1)-fold coordination mode, was found in the solid state. This additional binding is the first indication that the extra donor might also occupy a free coordination site in the excited-state complex, modifying the nature of the excited states and their respective deactivation processes. Therefore, the electrochemical and photophysical properties of all novel complexes (in total 13) were studied in detail to assess the potential of these photosensitizers for future applications within solar energy conversion schemes. Finally, the photostabilities and a potential degradation mechanism were analyzed for representative samples.