Triboluminescence (TL) is the emission of light induced by the application of mechanical energy to a solid. It links the spectroscopic, structural, mechanical, and electrical properties of solids. Here, materials of ZnS doped with various contents of Mn2+ were investigated. It was shown that they all have favorable triboluminescent property. The effects of the content of Mn2+, the sintering temperature and time on the luminescent property of ZnS:Mn were discussed. It was found the ZnS doped with 1.2% Mn2+ exhibited the strongest TL intensity among the materials investigated. The growth conditions were obtained through experiments, and ZnS:Mn with highly efficient triboluminescence was prepared. The mechanism of triboluminescence is proposed as follows: the electrons are excited from ground state to excited state by mechanic energy, then recombines with holes and give lights. The broad range of exciting energy may contribute to the high triboluminescent efficiency.