Purpose. To improve existing methods for safe routing when transporting hazardous materials as well as waste products. Methodology. Methods of mathematical modeling, methods of statistics, methods for predicting risks and long-term environmental consequences are used. Taking into account time factors, the distribution of population into different sections of highways is considered. Findings. Parameters of the transport network and their influence on the magnitude of the risk of an emergency situation and possible accidents in the transportation of hazardous waste (THW) are established in the work. An analysis is conducted of dangerous effects that can be caused by THW taking into account the parameters of road, transport network, type and modes of transport, and others. In order to minimize the risk of accidents during THW, it is proposed to use appropriate approaches and criteria K1 and K2, which take into account the lowest values of dangerous effects on the person during the transportation time, which allow evaluating the safety of the transportation system and the selected route, whereas their product takes into account all the possible main factors of the transportation system. Typical road and rail transport schemes have been identified to ensure a minimum number of accidents and reduce environmental and human hazards. Originality. Approaches are improved to transportation of dangerous goods by motorway and railroad, in particular, the parameters of curvature and inclination of the road, availability of settlements and bridges, meteorological conditions and traffic congestions, which improves the efficiency and safety of transportation of dangerous substances and materials. Practical value. The original mathematical models of mapping the route for transporting dangerous substances are offered while the existing ones are improved. The results of the research can be used by transport companies, public authorities in the transportation of hazardous substances and logistics and non-hazardous industries. [ABSTRACT FROM AUTHOR]