An important aspect of railroad environmental risk management involves tank car transportation of hazardous materials. This paper describes a quantitative, environmental risk analysis of rail transportation of a group of light, non-aqueous-phase liquid (LNAPL) chemicals commonly transported by rail in North America. The Hazardous Materials Transportation Environmental Consequence Model (HMTECM) was used in conjunction with a geographic information system (GIS) analysis of environmental characteristics to develop probabilistic estimates of exposure to different spill scenarios along the North American rail network. The risk analysis incorporated the estimated clean-up cost developed using the HMTECM, route-specific probability distributions of soil type and depth to groundwater, annual traffic volume, railcar accident rate, and tank car safety features, to estimate the nationwide annual risk of transporting each product. The annual risk per car-mile (car-km) and per ton-mile (ton-km) was also calculated to enable comparison between chemicals and to provide information on the risk cost associated with shipments of these products. The analysis and the methodology provide a quantitative approach that will enable more effective management of the environmental risk of transporting hazardous materials.