Here, we present the synthesis and spectroscopic studies of a novel photocatalyst dyad employing a perylene (Per) photosensitizer (phenPer = 5-(perylen-3-yl)-1,10-phenanthroline) and a catalytic RhCp* moiety, namely Rh III phenPer ([(phenPer)Rh(Cp*)Cl]Cl, see Fig. ). A number of previous studies reports on the incorporation of [(N^N)Rh(Cp*)Cl] + units (N^N = phen (1,10phenanthroline) or bpy (2,2'-bipyridine)) in heterogeneous or homogenous catalytic systems. In contrast, only a few examples reveal intramolecular assemblies of RhCp*, i.e., with a Ru II polypyridine sensitizer or organic chromophores. To unravel the light-induced processes in Rh III phenPer we applied steady-state and transient absorption spectroscopy. The principal applicability of Rh III phenPer as a thermal and light-driven reduction catalyst for regioselective NAD + (nicotinamide adenine dinucleotide) hydrogenation forming NADH was investigated.