Urban eco-environmental degradation is becoming inevitable due to the extensive urbanization, population growth, and socioeconomic development in China. One of the traffic arteries in Shenzhen is an urban expressway that is under construction and that runs across environmentally sensitive areas (ESAs). The environmental pollution from urban expressways is critical, due to the characteristics of expressways such as high runoff coefficients, considerable contaminant accumulation, and complex pollutant ingredients. ESAs are vulnerable to anthropogenic disturbances and hence should be given special attention. In order to evaluate the environmental sensitivity along this urban expressway and minimize the influences of the ongoing road construction and future operation on the surrounding ecosystem, the environmental sensitivity of the relevant area was evaluated based on the application of a geographic information system (GIS). A final ESA map was classified into four environmental sensitivity levels; this classification indicates that a large proportion of the expressway passes through areas of high sensitivity, representing 11.93 km or 52.3% of the total expressway, and more than 90% of the total expressway passes through ESAs. This study provides beneficial information for optimal layout schemes of initial rainfall runoff treatment facilities developed from low-impact development (LID) techniques in order to minimize the impact of polluted road runoff on the surrounding ecological environment.