We report the results of investigation of the interaction of silver with presynthesized ZnS nanoparticles (NPs) that was stabilized by cetyl trimethyl ammonium bromide (CTAB). The photoluminescence properties of ZnS NPs were followed in the presence of Ag+ ions, Ag NPs and by the synthesis of Ag@ZnS core-shell nanoparticles. We observed that CTAB stabilized ZnS NPs emitted broadly in the region from 350–450 nm, when excited by 309 nm light. In the presence of Ag+ ions the emission peak intensity up to 400 nm was reduced, while two new and stronger peaks at 430 nm and 550 nm appeared. Similar results were obtained when Ag NPs solution was added to ZnS solution. However, when Ag@ZnS NPs were synthesized, the emission in the 350–450 nm region was much weaker in comparison to that at 540 nm, which itself appeared at a wavelength shorter than that of Ag+ ion added ZnS NPs. The observations have been explained by the presence of interstitial sulfur and Zn2+, especially near the surface of the nanocrystals and their interaction with various forms of silver. In addition, our observations suggest that Ag+ ions diffuse into the lattice of the preformed ZnS NPs just like the formation of Ag+ doped ZnS NPs and thus changes the emission characteristics. We also have pursued similar experiments with addition of Mn2+ ions to ZnS and observed similar results of emission characteristics of Mn2+ doped ZnS NPs. We expect that results would stimulate further research interests in the development of fluoremetric metal ion sensors based on interaction with quantum dots.