When the pumping operation of pumped storage unit suffers from power outage, the hydraulic transient poses a serious threat to the safe operation of the unit and its pressure pipeline system. For high-head pumped storage power station (PSPS), the water hammer pressure (WHP) and rotational speed rise ratio (RSRR) of each hydraulic unit will be increased during the pump outage condition. In order to limit the fluctuation of rotational speed and WHP in power-off condition, optimizing and choosing a reasonable guide vane closure scheme (GVCS) is an economic and efficient means to improve the dynamic characteristics of pumped storage unit. On the basis of the calculation model of the transition process of single tube-double unit type of a high-head PSPS, an optimization model of GVCS balancing WHP and RSRR objectives is established. Furthermore, the two-stage broken line and three-stage delayed GVCSs are applied to the pump outage condition, and the nondominated sorting genetic algorithm-II (NSGA-II) is introduced to calculate the optimal solution set under different water heads and different closure schemes. For four typical water heads, the multiobjective optimization results of the closure law show that the two-stage broken line law has a better Pareto front under high water head, while the three-stage delayed law has a better performance under low water head. Furthermore, through the results of transition process of typical schemes, the adaptability of GVCS and water head is analyzed. The method proposed in this paper can make the RSRR not more than −0.89, and the three-stage delayed law can even make the RSRR only −0.01. Methods of this paper provide a theoretical basis for optimum guide vane closure mode setting of PSPS.