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This paper proposes a method for the optimal black-start reserve water of pumped storage. When pumped storage provides black-start ancillary service for power system, some capacity in the upper reservoir must be reserved and then the peak-load shaving benefit of pumped storage plant would be influenced. In order to make pumped storage plant bring the largest benefits to power system, a mathematical model and the solving method of the optimal black-start reserve water are proposed. The model comprehensively considers black-start benefit and peak-load shaving benefit. According to the data from black-start field test, the optimal black-start reserve water of Taishan pumped storage is calculated to illustrate the proposed method and quantify the benefits of pumped storage plant. The strategy and the method can be applied in other power grids whose power plants almost all consist of thermal generators and use pumped storage as black-start source.