As an advanced energy storage technology, the compressed CO2 energy storage system (CCES) has been widely studied for its advantages of high efficiency and low investment cost. However, the current literature has been mainly focused on the TC-CCES and SC-CCES, which operate in high-pressure conditions, increasing investment costs and bringing operation risks. Meanwhile, some studies based on the phase-change CO2 energy storage system also have had the disadvantages of low efficiency and the extra necessity of heat or cooling sources. To overcome the above problems, this paper proposes an innovative compressed CO2 phase-change energy storage system. During the energy charge process, molten salt and water are used to store heat with a smaller temperature difference in heat exchangers, and high-pressure CO2 is reserved in liquid form. During the energy discharge process, throttle expansion is applied to realize the evaporation at room temperature, and CO2 absorbs the reserved heat to improve the power capacity in the turbine and the system energy storage efficiency. The thermodynamic and exergoeconomic studies are performed firstly by using MATLAB. Then, the parametric study based on energy storage efficiency, system unit product cost, and exergy destruction is analyzed. The results show that energy storage efficiency can be improved by lifting liquid CO2 pressure as well as compressor and turbine isentropic efficiencies, and CO2 evaporation pressure has the optimal pressure point. The system unit product cost can be reduced by decreasing liquid CO2 pressure and compressor isentropic efficiency, while CO2 evaporation pressure and turbine isentropic efficiency both have optimal points. Finally, the optimization of two performances is performed by NSGA-II, and they can reach 75.30% and 41.17 $/GJ, respectively. Moreover, the optimal energy storage efficiency is obviously higher than that of other energy storage technologies, indicating the great advantage of the proposed system. This study provides an innovative research method for a new type of large-scale energy storage system.