The study is related to the improvement of the safety methodology for the application of dangerous chemical substances and the development of binding action and response algorithms for officials of the State Fire and Rescue Service, who first arrive at the sites of the event with the presence of dangerous chemical, biological, radioactive and explosive substances. The safety methodology is intended to quickly provide the primary information needed to the rescue team in the context of action at the site, which will allow for the possible negative effects and risks to the environment to be minimized as soon as possible and more effectively. Events with the presence of dangerous substances can potentially lead to major human casualties, significant material losses and also irreversible risks to the environment, since the elimination of the consequences of pollution can take several hours to a few months and even years. The examination of the regulatory enactments determining the responsibility of the services and the regulatory documents governing action, revealed the limits of the cooperation and responsibility of the services, as well as the division of functions in response to events with the HS, as well as the assessment of the internal regulatory enactments of the services involved in cooperation, allowing a better assessment of their resources and capacity in the event of an emergency. Also, the manuals, instructions and action algorithms of the European services were also evaluated, which were taken into account, tested and used in cooperation between different services in the event of an emergency with dangerous substances. Based on the results of the study, an instruction was developed which included primary information necessary for the head of rescue works, in the context of action at the site, which will allow for the earliest and more efficient reduction of the potential adverse effects and risks to the environment caused by the event. An instruction will be included in the training course programme for the preparedness of fire rescuers and future rescue managers, which will significantly facilitate not only the implementation of the work process but also improve the quality of the training process of the College of Fire Safety and Civil Protection according to modern competencies.