Current techniques and methods of risk assessment in the field of hazardous substances road transportation are oriented especially towards assessing the impacts of potential accidents on population and the environment. However, every subject affected has different preferences arising from the nature of his activities. While a carrier prefers maximum profit arising from safety transport, public administration authorities prefer ensuring maximum safety of population and other public estates and properties. At the same time, it is necessary to point out that current legal regulations make a significant drawback in the field of ensuring safety of hazardous substances road transportation. The above mentioned legal regulations do not require risk assessments from the road carriers of hazardous substances. Therefore, carriers do not carry out such assessments, as the data gained from accessible techniques and methods do not provide them with requested information. Applying the multi-criteria preference risk assessment of hazardous substances road transportation brings a suitable solution to the current situation, as it lies in setting criteria by considering real threats as well as all potential areas of their impact. Subsequent implementation of weight coefficients enables the assessor to prefer his concerns, while the final risk listing provides him with requested information regarding his activities. Realizing such assessment brings complex increase in preventive safety measures in hazardous substances road transportation, since it enables the carrier to realize not only primary risks connected with possible economic loss, but also secondary risks related to the impact on population and other public estates and properties.