Here, we report the synthesis of monolayer protected, luminescent and atomically precise silver sulfide (Ag₂S) clusters. Cluster formation was studied by varying the conditions of the reaction. Matrix assisted laser desorption ionization mass spectrometry (MALDI MS) was used to monitor the growth of clusters to nanoparticles (NPs). Clusters of different nuclearity were obtained at a lower temperature, and were efficiently separated by thin layer chromatography (TLC). One of the clusters was assigned as Ag₁₅₈S₇₉(SBB)₃₂, where SBB is 4-tert-butylbenzyl mercaptan.