Safety is a stumbling block to the applications of the lithium-ion batteries in electric vehicles, especially under the abuse condition of overcharge. Much research on preventing overcharge is being done to ensure the safety of the lithium-ion batteries. However, almost no strategy can balance the safety and the performance of the lithium-ion batteries well for overcharge protection. No data to support the longer term effectiveness of the used strategy were presented in the previous reports. Herein, a new electrolysis reaction, synergistic electrolysis of the organic/inorganic compounds (p-fluorotoluene and Li2CO3) is built for the first time as a controllable gas source to solve the overcharge problem of the prismatic lithium-ion battery cell with a current interrupt device inside. Overall, the balance point between the long-time performance and overcharge protection can be well achieved using the synergistic electrolysis.