Hazardous materials routing constitutes a critical decision in mitigating the associated transportation risk. This paper presents a decision support system for assessing alternative distribution routes in terms of travel time, risk and evacuation implications while coordinating the emergency response deployment decisions with the hazardous materials routes. The proposed system provides the following functionalities: (i) determination of alternative non-dominated hazardous materials distribution routes in terms of cost and risk minimization, (ii) specification of the hazardous materials first-response emergency service units locations in order to achieve timely response to an accident, and (iii) determination of evacuation paths from the impacted area to designated shelters and estimation of the associated evacuation time. The proposed system has been implemented, used and evaluated for assessing alternative hazardous materials routing decisions within the heavily industrialized area of Thriasion Pedion of Attica, Greece. The implementation of the aforementioned functionalities is based on two new integer programming models for the hazardous materials routing and the emergency response units location problems, respectively. A simplified version of the routing model is solved by an existing heuristic algorithm developed by the authors. A new Lagrangean relaxation heuristic algorithm has been developed for solving the emergency response units location problem. The focus of this paper is on the exposition of the proposed decision support system components and functionalities. Special emphasis is placed on the presentation of the two new mathematical models and the new solution method for the location model.