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Petroleum industry is a high-risk industry and accidents in petroleum often cause significant casualties and economic losses. Heavy gas dispersion and the blowout accident of a natural gas well with H2S gas are two kinds of toxic gas release in petrochemical industry with high frequency. Therefore it is necessary to develop an emergence decision support system for toxic gas release. In this paper, a GIS-based emergency decision support system of toxic gas release is constructed, and gas diffusion models and the algorithms to select optimal path are integrated in the system. A suitable gas diffusion model is selected to simulate toxic gas spread risk dynamically and the time costs of people evacuation and emergency rescue is analyzed using optimal path algorithm. Combining analysis of the spread areas of toxic gas and the time costs of different evacuation and emergency rescue path, emergency decision support system can establish an emergency decision and response with moderate risk and time costs, which will be effective for the rescue work.