Hazardous industrial sites have always represented a threat for the community often provoking major accidents overcoming the boundaries of the plants and affecting the surrounding urban areas. If the industrial sites are located in natural hazard-prone areas, technological accidents may be triggered by natural events, generating so-called na-tech events which may modify and increase the impact and the overall damage in the areas around them. Nevertheless, natural and technological hazards are still treated as two separate issues, and up to now the methods for na-tech risk assessment have been developed mainly for specific natural hazards, generally restricted to some plant typologies and to the area of the plant itself. Based on a review of the current na-tech literature, this article illustrates a risk assessment method as a supporting tool for land use planning strategies aimed at reducing na-tech risk in urban areas. More specifically, a multi attribute decision-making method, combined with fuzzy techniques, has been developed. The method allows planners to take into account, according to different territorial units, all the individual na-tech risk factors, measured through both quantitative and qualitative parameters, while providing them with a na-tech risk index, useful to rank the territorial units and to single out the priority intervention areas. The method is designed to process information generally available about hazardous plants (safety reports), natural hazards (hazard maps) and features of urban systems mainly influencing their exposure and vulnerability to na-tech events (common statistical territorial data). Furthermore, the method implemented into a GIS framework should easily provide planners with comparable maps to figure out the hazard factors and the main territorial features influencing the exposure and vulnerability of urban systems to na-tech events. The method has been tested on a middle-sized Municipality in the Campania Region, identified as 2nd class seismic zone, according to the Ordinance 3274/2003, in which a LPG storage plant, classified as a plant with major accident potential by the Seveso II Directive (art. 9), is located just within the city core