Within this research, a methodology is developed aiming to the optimization of locating emergency services along the road axes in order to minimize both the maximum and the average access time at the accident scene.  The proposed methodology can be used for the redefinition of the operational responsibility areas of the existing emergency services’ stations as well as for the definition of new necessary stations.  The originality of the proposed methodology lies to the fact that for the calculation of operational responsibility areas, the traffic and related accidents are taken into consideration additionally to the related distances, allowing for the identification of solutions meeting better a greater number of road accidents.  The methodology developed for the identification of the optimum distribution of Fire and Rescue Services along the two main road axes of Greece (Patras-Athens-Thessaloniki-Evzoni) and Via Egnatia.