N‐terminally Fmoc‐protected dipeptide, Fmoc‐Val‐Asp‐OH, forms a transparent, stable hydrogel with a minimum gelation concentration of 0.2 % w/v. The gelation property of the hydrogel was investigated by using methods such as transmission electron microscopy, field‐emission scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy. The silver‐ion‐encapsulating hydrogel can efficiently and spontaneously produce fluorescent silver nanoclusters under sunlight at physiological pH (7.46) by using a green chemistry approach. Interestingly, in the absence of any conventional reducing agent but in the presence of sunlight, silver ions were reduced by the carboxylate group of a gelator peptide that contains an aspartic acid residue. These clusters were investigated by using UV/Vis spectroscopy, photoluminescence spectroscopy, high‐resolution transmission electron microscopy (HR‐TEM), atomic force microscopy (AFM) and X‐ray diffraction (XRD) studies. Mass spectrometric analysis shows the presence of a few atoms in nanoclusters containing only Ag2. The reported fluorescent Ag nanoclusters show excellent optical properties, including a very narrow emission profile and large Stokes shift (>100 nm). The reported fluorescent Ag nanoclusters within hydrogel are very stable even after 6 months storage in the dark at 4 °C. The as‐prepared hydrogel–nanocluster conjugate could have applications in antibacterial preparations, bioimaging and other purposes.