In order to further improve the economic benefits of pumped storage power stations participating in the electricity market, an intra-day real-time optimal scheduling method for pumped storage power stations based on the evaluation of electricity energy value is proposed. The operation plan of pumped storage under an electricity market transaction day is divided into multiple periods, and the operation state is formulated and adjusted in real time for the operation conditions of each period. A hydropower-real-time value assessment model based on the opportunity generation revenue assessment of the remaining adjustable capacity of the pumped storage power station is established. The proposed model takes the maximization of the revenue of participating in the electricity spot market and the auxiliary service market as the objective function, and takes into account the necessary constraints such as carbon emission constraints, adjustable capacity constraints, power station operation power constraints, and power station participation in the electricity market state constraints. Then, by comparing the marginal opportunity generation income and the electricity market price of the remaining adjustable capacity, the real-time optimal scheduling strategy is used to rollingly formulate the operating state of the pumped storage power station in the current period. The simulation results show that compared with the traditional day-ahead optimal scheduling method, the proposed method can effectively improve the revenue of pumped storage power stations participating in the electricity market and to achieve carbon emission reduction, which verifies the correctness and effectiveness of the model.