Owing to the atomic precession and exotic photophysical properties, silver cluster assembled materials (CAMs) have been explored for use as functional nanomaterials in recent years. Although a small number of thiolate protected silver CAMs have previously been investigated, the synthesis of thiol-free analogues and their solubility remain challenging. Here, the structure–property correlation of a newly synthesized one-dimensional phenyl phosphonate protected [Ag₂(PhPO₃H)₂(apy)₂], (in which, 4,4′-azopyridine = apy) CAM is demonstrated. The multifunctional surface protecting ligand is strategically attached to the core for the first time to tailor the solubility, structural stability and charge transfer mechanism. The small size of the cluster building blocks, along with the choice of organic linker molecules, efficiently stabilize the structure via intra-chain π–π stacking while inter-chains π–π interactions create a two-dimensional supramolecular architecture. The advantageous band structure associated with the charge transfer phenomenon and the high structural stability of the material are guided to explore the sustainable photoresponsive character of this CAM, resulting in the generation of an 82 nA photocurrent. Additionally, the unprecedented water solubility, which is very rare for this class of material, provides opportunities for use in biomedical imaging applications. The measured photoacoustic signal strength confirms the blood vessel mimicking capabilities of the portrayed material at a depth of approximately 3 mm inside chicken breast tissue.