As a new energy infrastructure, the photovoltaic-storage integrated charging station (PSICS) not only enables orderly EV charging but also promotes the green economic transition of power systems. First, topological structure and operational mechanism of PSICS are systematically elaborated; Then, a PSICS-EV collaborative optimization framework based on Stackelberg game theory is established. By coordinating the multi-agent interest demands of distribution network operators, charging station operators, and EV users, a bi-level scheduling model considering multi-timescale characteristics is developed. A hybrid solution strategy combining heuristic algorithms with commercial solvers is employed for model resolution. The results show that the proposed model can effectively improve the operational economy of the PSICS, reduce the charging costs for EVs, and alleviate the power supply pressure on the distribution network.