The invention discloses an expressway deck runoff treatment and accident emergency system, which comprises the following parts: a treatment unit, a remote proximity card arranged on a hazardous chemical transportation vehicle, card readers arranged at front and back ends of a bridge, a control system and each electromagnetic valve controlled by the control system. The system disclosed by the invention is used for carrying out oil, water and solid separation on rainwater runoff on the deck, the occupied space is small, the efficiency is high, the system can be arranged nearby at two sides of the bridge, sewage can be treated in time, the quality of directly discharged water can meet requirements of environmental protection, and the system is particularly suitable for expressway bridges. The system can also meet the requirements of environmental protection in extreme severe weather such as rainstorm. A conducting valve is controlled to be opened and closed in three different work states: the normal state, the preparation state and the emergency state, so pre-warning and preparation for dealing with accidents can be realized; even under the condition of no monitoring by personnel, any chemical does not leak after a leakage accident of hazardous articles occurs, and risks of polluting water sources such as rivers and lakes are eradicated.