Noble metal thiolate nanoclusters are a new class of nanomaterials with molecular-like properties such as high dispersibility and fluorescence in the visible and infrared spectral region, properties highly requested in biomedicine for imaging, sensing and drug delivery applications. We report on three new silver phenylethane thiolate nanoclusters, differing for slight modifications of the preparation, i.e., the reaction solvent and the thiolate quantity, producing changes in the nanocluster composition as well as in the fluorescence behavior. All samples, excited in the range 250-500 nm, emit around 400 and 700 nm differing in the emission maxima and behavior. The silver thiolate nanoclusters have been characterized by way of C, H, S elemental analyses and Thermal Gravimetric Analysis (TGA) to determine the nanocluster composition, Scanning Transmission Electron Microscopy (STEM) to investigate the nanocluster morphology and UV-Vis and fluorescence spectroscopy to study their optical properties.