Abstract: The joint operation of photovoltaic power stations and energy storage systems can reduce the uncertainty of power output from the power supply side and improve the stability of the power grid. The current application scenarios for solar energy storage power stations are relatively single, making it difficult to simultaneously consider primary and secondary frequency regulation and joint electricity sales. In response to this issue, this paper proposes a multi-scenario compatible day-ahead rolling optimization operation strategy that considers the electricity market and primary and secondary frequency regulation services. Firstly, the characteristics of primary and secondary frequency modulation signals will be analyzed, and a collaborative optimization strategy framework for hybrid energy storage in photovoltaic power plants will be proposed under multi-application scenario scheduling resolution. Then, to maximize the joint revenue of the station, a daily optimization model is established that considers the secondary frequency regulation capacity of energy storage. In the intraday stage, the actual output priority of each scenario is considered, and a rolling optimization solution is obtained to obtain the operation plan of the energy storage system. Using actual data from a photovoltaic power station in Daqing, Heilongjiang Province, simulation verification was conducted, and sensitivity analysis was conducted on the model. The example shows that the optimization strategy proposed in this paper can unleash the scheduling potential of different energy storage resources, effectively improve the accuracy of power station reporting and frequency regulation ability.