The purpose of this study is to demonstrate a methodology for quantification of high emissions hot spots along roadways based upon real-world, on-road vehicle emissions measurements. An emissions hot spot is defined as a fixed location along a corridor in which the peak emissions are statistically significantly greater by more than a factor of 2 than the average emissions for free-flow or near free-flow conditions on the corridor. A portable instrument was used to measure on-road tailpipe emissions of carbon monoxide, nitric oxide, hydrocarbons, and carbon dioxide on a second-by-second basis during actual driving. Measurements were made for seven vehicles deployed on two primary arterial corridors. The ratio of average emissions at hot spots to the average emissions observed during a trip was as high as 25 for carbon monoxide, 5 for nitric oxide, and 3 for hydrocarbons. The relationships between hot spots and explanatory variables were investigated using graphical and statistical methods. Average speed, average acceleration, standard deviation of speed, percent of time spent in cruise mode, minimum speed, maximum acceleration, and maximum power have statistically significant associations with vehicle emissions and influence emissions hot spots. For example, stop-and-go traffic conditions that result in sudden changes in speed, and traffic patterns with high accelerations, are shown to generate hot spots. The implications of this work for future model development and applications to environmental management are discussed.