Abstract: A single operation mode of the energy storage system is difficult to meet various technical requirements of a photovoltaic-storage charging station. In view of this problem, this paper proposes an optimal operation strategy of the energy storage system in a photovoltaic-storage charging station considering multi-mode integration. Firstly, typical operation modes of the energy storage system in a photovoltaic-storage charging station are analyzed, and multi-mode integration of the energy storage system is designed on this basis. Secondly, operation models of the energy storage system in the photovoltaic-storage charging station under different modes are established to further propose an optimal operation strategy of the energy storage system in the photovoltaic-storage charging station with multi-mode integration. Finally, the proposed strategy is simulated and experimentally analyzed based on 24 h operation curves of a photovoltaic-storage charging station in Shanghai. The results show that the proposed strategy can reduce load fluctuation and energy-balance cost of the energy storage system, thus improving operating benefits of the photovoltaic-storage charging station.