Photoredox catalysts are able to drive reactions with high kinetic or thermodynamic barriers by harnessing the energy of light. This in-situ preparation of highly oxidizing or reducing reagents from stable precursors allows gentler more selective reaction conditions, opening the doors to many new reactions such as the processing of lignin into stock chemical species to aryl-dehalogenation reactions. Cyclometalated (C^N) and polypyridyl (N^N) complexes of d 6 metals are some of the most promising transition metal photoredox catalysts to date. Heteroleptic compounds incorporating (C^N) and (N^N) ligands, as in [Ir(ppy) 2 (bpy)] + complexes, benefit from independent tunability of HOMO and LUMO levels via ligand architecture. Yet, the relationship between structural/environmental perturbations and changes in the intricate excited-state manifold of [Ir(ppy) 2 (bpy)] + complexes are hard to capture with existing spectroscopies, making it commensurately difficult to understand all the factors that modulate their photoredox activity. Tuning of the redox potentials, absorption energy, excited-state lifetime, and quantum yield, are well known criteria, but other factors can play an important role. For instance, recent work suggests that the size and polarity of the counter-ion effects the efficiency of the catalytic cycle, . While many reports note spectral changes due to ion-pairing in common photoredox catalysts, there are currently no direct quantitative methods that can probe the ground and excited-state electron density distribution to understand how ion pairing influences the excited state structure and evolution. Here, we introduce a modern implementation of time-resolved dielectric-loss spectroscopy (TRDL) to investigate how counter-ion identity influences the excited-state charge distribution within an important photoredox catalyst, [Ir[dF(CF 3 )ppy] 2 (dtbpy)]X. We find large differences in both the ground and excited-state dipole moments depending on