A deep understanding of driver behavior is an important step to improve road safety and environmental performance. Volatility can be defined as the extent of variations in driving, which can be characterized by accelerations/braking, lane change, and unusual high speed for roadways conditions. There is a lack of knowledge on what concerns the relationship between driver's volatility and exhaust emissions and how driving volatility can be used as safety eco-indicator. This article explores a driving volatility concept for assessing tailpipe emissions and driving behavior classification. For that purpose, an empirical approach that combined vehicle activity and emission rates for light duty vehicles was used. Field measurements were collected from four probe vehicles in one partly urban/rural, and two highway routes using Portable Emission Measurement Systems, Global Positioning System receivers, and On-board Diagnostic scan tool, to measure real-world tailpipe emissions, position and engine activity data. Accelerationbased parameters, including relative positive acceleration and mean of positive acceleration, acceleration, vehicular jerk, and power demand thresholds were used to detect differences in emissions for different driving styles. Results indicated that vehicular jerk impacted carbon dioxide and nitrogen oxides per unit distance regardless of driving style and route type, especially from negative to null jerk values and during positive accelerations. There is potential to incorporate the analyzed thresholds into a driver decision support algorithm by considering safety and environmental aspects through warning messages.