The accidents such as explosion, leakage, poisoning and fire happened constantly in dangerous goods' transportation. The consequences of the accidents are serious. This article has statistically analyzed 485 transportation accidents of dangerous goods. It shows that the main reason causing dangerous goods accidents is road traffic accidents. The key to ensure the seasonable rescue is effective visual monitor using GPS, modern communication technology, GIS to dangerous goods transport vehicles. So we construct the transportation monitoring system. When the accident inevitably occurs, we propose the rescue mission and response program. Only effective monitoring and timely rescue, can we reduce the rate of accidents and ensure our safety.