Concern for natural hazard-triggered technological disasters (Natech disasters) in densely populated and industrialized areas is growing. Residents living in urban areas subject to high natural hazard risk are often unaware of the potential for secondary disasters such as hazardous materials releases from neighboring industrial facilities, chemical storage warehouses or other establishments housing hazardous materials. Lessons from previous disasters, such as the Natech disaster during the Kocaeli earthquake in Turkey in 1999 call for the need to manage low frequency/high consequence events, particularly in today’s densely populated areas. However, there is little guidance available on how local governments and communities can assess Natech risk. To add to the problem, local governments often do not have the human or economic resources or expertise to carry out detailed risk assessments. In this article, we propose a methodology for preliminary assessment of Natech risk in urban areas. The proposed methodology is intended for use by local government officials in consultation with the public. The methodology considers possible interactions between the various systems in the urban environment: the physical infrastructure (e.g., industrial plants, lifeline systems, critical facilities), the community (e.g., population exposed), the natural environment (e.g., delicate ecosystems, river basins), and the risk and emergency management systems (e.g., structural and nonstructural measures). Factors related to vulnerability and hazard are analyzed and qualitative measures are recommended. Data from hazardous materials releases during the Kocaeli, Turkey earthquake of August 17, 1999 are used as a case study to demonstrate the applicability of the methodology. Limitations of the proposed methodology are discussed as well as future research needs.