For optimizing light-driven catalytic processes, lightmediated multi-electron transfer dynamics in molecular dyads need to be studied and correlated with structural changes focusing on the catalytically active metastable intermediates. Here, spectroelectrochemistry has been employed to investigate the structure dependent photoelectron transfer kinetics in catalytically active intermediates of two Ru-Rh-catalysts for light-driven NAD+ reduction. The excited state reactivity of short-lived intermediates was studied along different photoreaction pathways by resonance Raman and time-resolved transient absorption spectroelectrochemistry with sub-ps time resolution under operando conditions. The results demonstrate for the first time, how the bridging ligand serves as an (multi-)electron storage structure, mediates the strength of the electronic coupling of catalytic and photocenter and impacts the targeted electron transfer as well as parasitic electron-transfer kinetics.