The development of new energy vehicles has driven the maturity of the lithium-ion battery industry, resulting in rapid growth in the mobile energy storage vehicle (MESV) industry. Considering the involvement of mobile energy storage vehicles in peak load shaving and auxiliary services for high-power end-users, research is being conducted on the optimization of MESV paths and charging/discharging strategies. Firstly, the operation mode of MESVs storage is analyzed to establish an optimal scheduling framework for MESVs considering peak load shaving and anxiliary services. Secondly, the billing method based on demand charge tariff (DCT) is included in the target model considering the path selection, charging/discharging power limitation and state of charge (SOC) constraints. Then, with the aim of maximizing the overall revenue of MESVs in peak load shaving and auxiliary services, a model is constructed for optimizing the selection of MESV paths and charging/discharging strategies. Furthermore, the impact of DCT billing on user load curve is analyzed. Finally, taking the actual road network of a city as an example, the feasibility and effectiveness of the proposed method are verified by comparative analysis of the example.