The concentration of Residual Chlorine (RC) frequently violates the standard in situations of urban water distribution system with large water supply area and long time of distribution.If chlorine dosage increases within water treatment plant, although RC in distribution system could meet water quality standard, Disinfection By-Products (DBPs) such as hydrocarbon halide rises.In the paper, a mathematical model of chlorine allocation optimization was presented based on reaction kinetics mechanism and optimization theory to solve the problem.The model includes the objective function of minimizing annual operation cost and constraints of RC standard and rational chlorination station distribution, and solving by 0-1 Integer Programming (IP).The model had been applied to a real water distribution system.The simulation results of the model showed that adding chlorine in water distribution system remarkably improved water quality and reduced the operation cost by 49.3% per year less than chlorine dosed only in water treatment plant to meet RC standard.The results prove adding chlorine in water distribution system based on the model can bring both technological and economic advancement.