Hollow Ag2S spheres have been prepared via hydrolyze reaction of Ag2S2O3, which formed from the reaction of AgNO3 with Na2S2O3, in cyclohexane/water/polyglycol emulsion system. It was found that the component of the reaction system has a significant influence on the formation of hollow Ag2S spheres. The possible formation mechanism of the hollow Ag2S spheres in the emusion system was also discussed.