A novel chloride volatilization process for the treatment of jarosite residue stored in Serbia is developed. In this process, valuable metals such as lead, zinc, copper, silver and indium are chlorinated and volatilized with the addition of chlorinating agent. Iron is enriched in the slag and used in iron making system after magnetic separation or other methods. Sulfur combines with calcium and forms a stable calcium sulfate to avoid the production of sulfur dioxide. The influence of reducing agent, chlorinating agent and temperature on volatilization rate of zinc, lead, copper, silver and indium are investigated. The results show that: the addition of chlorinating agent, reducing agent and temperature have an effect on the metal volatilization rate; the addition of chlorination agent improves the volatilization rate of lead, zinc, copper, silver and indium; and the addition of reducing agent further improve the metal recovery rate. Under the recommended conditions, the volatilization rate of each element is zinc 98.26%, lead 99.88%, copper 97.32%, indium 58.73% and silver 95.22% respectively. The chloride volatilization process not only transforms jarosite residue into general solid waste, but also comprehensively recovers valuable metals such as lead, zinc, copper, silver, indium and iron, etc. The process completely solves the potential pollution of jarosite residue and has good economic benefits.