Moreover, ATP bears negatively charged phosphates as well as an aromatic π-conjugated adenine ring allowing, multiple electrostatic, π-π and hydrogen bonding interactions, thus making it prone to be engaged in supramolecular self-assembled systems . Several stimuliresponsive ATP-based supramolecular systems have thus been developed but for only a few specific stimuli. One strategy consisted in exploiting ATP as an enzyme substrate to build enzyme-responsive assemblies. This was achieved in particular using phosphatase to control the fluorescence or chirality of the assemblies . Another approach explored the chelating properties of ATP with metals to develop ion-responsive supramolecular structures but these investigations were limited to small-sized complexes . Besides enzymes and metals, light constitutes a highly desired trigger to control self-assemblies due to its precise spatiotemporal control, tunability (wavelength, power) and remote character . Light-responsive ATP-based systems to photochemically control the release of this nucleotide have been described but this involved photocleavable bounds, therefore precluding any photo-reversible response . To our knowledge, photoreversible supramolecular assemblies involving unmodified ATP have yet to be demonstrated. To reach such a goal, azobenzene-containing molecules constitute promising co-assembly partners as they have been successfully exploited in photocontrolled supramolecular assemblies for their robustness and for a rapid and reversible trans-cis photoisomerization . Cationic derivatives of azobenzene can be used in particular to electrostatically interact with negatively charged mono-or polynucleotides, a process that can be rendered photodependent through the polarity and/or geometric changes upon azobenzene trans/cis isomerization . This was used for instance to photocontrol phenomena such as DNA compaction , co-acervation , DNA intercalation or G-quadruplex formation . With the objective to build extended photoreversible ATP assemblies in water, and thus limit the possibility of precipitation, we avoided classical azobenzene cationic surfactants and opted instead for a hydrophilic azobenzene partner, choosing guanidium as the cationic group for its strong affinity for nucleotide phosphate groups, including those of ATP . We thus used AzoDiGua, a symmetric diguanidinium azobenzene derivative and photodependent DNA intercalator which was shown to co-assemble with guanosine monophosphate into photoswitchable and extended fluorescent crystals . In this work we coassembled AzoDiGua with ATP and observed the spontaneous formation in water of the first photo-reversible micrometer-sized supramolecular assemblies containing ATP. The self-assembled structures scattered light and exhibited fluorescence only in their assembled state, resulting in a reversible photoswitching of both turbidity and fluorescence. We also exploited the presence of ATP in the supramolecular structures to dynamically control their self-assembly by other stimuli, including metal ions and alkaline phosphatase (ALP) enzyme. With a combination of methods including optical microscopy, fluorescence spectroscopy, and electronic paramagnetic resonance (EPR), we characterized the reversibility, highly dynamic character and the switchable optical properties of these multi-stimuli responsive ATP/azobenzene-guanidinium assemblies of a new kind.