Overcharge is one of the most typical triggers leading to battery thermal runaway during real-worldvehicular operation. An in-depth exploration of the real-scenario-oriented failure mechanism of batteryovercharge is critical to safeguard the safe and durable operation of electric vehicles. With environmentalchanges and drivers’ random behaviors under real occasions considered, this paper demonstrates the multi-factor overcharge-to-thermal-runaway modelling theory based on electro-chemical thermal coupling analysis. A case study of a real-world electric vehicle that experienced an overcharge-causedthermal runaway accident is presented, and the pre-accident battery overcharge characteristics are dissected referring to the accident investigation reports. Furthermore, the multi-stage pre-accidentcharacterization is performed by dividing overcharge into three feature stages, such as charge, fully-charged instant, and overcharge. Various characterization parameters directly measurable and indirectly calculated are extracted, then a variable evaluation of the state of health degradation underovercharge is implemented. Moreover, a rudimentary probability model of overcharge-caused thermalrunaway is proposed combining all potential motivating factors, including environments and drivers’behaviors. This is the first of this kind to apply the actual accident case on overcharge-causedthermal runaway research, which can guide the battery overcharge protection to safeguard drivers andpassengers.