New Azo-AuNPs formulations certainly contribute to the ongoing research on the modulation of Azo isomerization. Expansion of the Azo excitation wavelengths into the red or near-infrared (NIR) range or modification of the Z-isomers lifetimes are valuable for neuronal activity control and photopharmacology. These goals can be achieved not only by synthetic modification of the chemical structures of Azo molecules but also by alternative strategies (often called indirect modifications) relying on electron transfer or intra-and intermolecular energy transfer. Alternative approaches are especially useful and appealing for advanced, multi-component, Azo-based systems. The alternative pathways modify and broaden the properties of the already existing Azo molecules beyond their intrinsic limitations and simultaneously maintain their profitable features, such as robustness. For a long time, AuNPs have been scarcely mentioned in the context of indirect modification of azobenzene photoswitching and, if so, only as multiphoton sensititzers. Recently, however, AuNPs have been recognized as factors modulating Azo Z-E isomerization in the dark (socalled thermal relaxation), presumably via electron transfer (eT), as proposed for the first time by Hallett-Tapley et al., and further supported in the ensuing research. However, these reports focused solely on the catalytic influence of spherical AuNPs on Azo isomerization in the dark.