The production, storage, and transportation of hazardous materials are processes of vital economic importance for any advanced and technologically complex society. Although the production and distribution of hazardous materials is associated with economic development, there is a significant potential danger to the natural and social environment in the event of their accidental release, a fact that prompts for the development and implementation of methods and techniques that aim to improve hazardous materials risk management decisions. The objective of this paper is to present a unified framework for developing a Decision Support System (DSS) for supporting a vital function of risk management, namely the management of emergency response operations. The proposed framework recognizes the peculiarities of the hazardous materials decision-making environment which is characterized by: (i) multiple stakeholders, i.e., persons and organizations involved in and affected by hazardous materials risk management decisions; (ii) lack of a formal management structure for monitoring and controlling in a unified manner all Emergency Response Resources; (iii) lack of clear distinction and fragmentation of responsibilities of the actors involved in risk management operations; and (iv) dynamic/real-time decisions, i.e., risk determinants change over time. The proposed framework was used in order to develop a DSS for managing emergency response operations for large scale industrial accidents in Western Attica, Greece.