The most important characteristic of major chemical accidents, from a societal perspective, is their tendency to produce off-site effects. The extent and severity of the accident may significantly affect the population and the environment of the adjacent areas. Following an accident event, effort should be made to limit such effects. Management decisions should be based on rational and quantitative information based on the site specific circumstances and the possible consequences. To produce such information we have developed an operational centre for managing large-scale industrial accidents. Its architecture involves an integrated framework of geographical information system (GIS) and RDBMS technology systems equipped with interactive communication capabilities. The operational centre was developed for Windows 98 platforms, for the region of Thriasion Pedion of West Attica, where the concentration of industrial activity and storage of toxic chemical is immense within areas of high population density. An appropriate case study is given in order to illuminate the use and necessity of the operational centre.