The synthesis and photophysical characterization of ZnS:Ag colloid are reported. The presence of mercaptoacetic acid has an important effect not only on the formation of doped and undoped ZnS but also on the photophysical properties. ZnS colloid doped with silver shows a strong green emission upon ultraviolet excitation, the intensity of which was enhanced significantly compared with that of the undoped colloid. The green emission was ascribed to a transition from a donor level such as anion vacancy to the levels of the Ag impurities.