Investigation at scene is the key issue to Scene Traffic Accident Reconstruction(TAR). Although the photogrammetry technique is widely applied in China due to its convenience and lower cost, it can only provide the final state of the traffic accidents. In this paper, a novel method based on the time difference of arrival (TDOA) technique was proposed to monitor the location of the vehicles passing the accident-prone section on the highway. The methodology of application of TDOA to the Traffic accident scene investigation was proposed, and the arrangement of sensors on the accident-prone sections of the selected freeway is discussed. Based on the coordinates collected by TDOA receivers, real-time position of the each vehicle moving on the accident-prone section could be extracted respectively and when the accidents happen, the traces of the vehicles involved would be obtained. It could be concluded that this method is important supplement to photogrammetry technique during accident scene investigation and could make the forensic judgment of accident responsibility more accurate.