Commercial transportation fuels are complex mixtures containing hundreds or thousands of chemical components, whose composition has evolved considerably during the past 100 years. In conjunction with concurrent engine advancements, automotive fuel composition has been fine-tuned to balance efficiency and power demands while minimizing emissions. Pollutant emissions from internal combustion engines (ICE), which arise from non-ideal combustion, have been dramatically reduced in the past four decades. Emissions depend both on the engine operating parameters (e.g. engine temperature, speed, load, A/F ratio, and spark timing) and the fuel. These emissions result from complex processes involving interactions between the fuel and engine parameters. Vehicle emissions are comprised of volatile organic compounds (VOCs), CO, nitrogen oxides (NO_x), and particulate matter (PM). VOCs and NO_x form photochemical smog in urban atmospheres, and CO and PM may have adverse health impacts. Engine hardware and operating conditions, after-treatment catalysts, and fuel composition all affect the amount and composition of emissions leaving the vehicle tailpipe. While engine and after-treatment effects are generally larger than fuel effects, engine and after-treatment hardware can require specific fuel properties. Consequently, the best prospects for achieving the highest efficiency and lowest emissions lie with optimizing the entire fuel–engine–after-treatment system. This review provides a chemical perspective on the production, combustion, and environmental aspects of automotive fuels. We hope this review will be of interest to workers in the fields of chemical kinetics, fluid dynamics of reacting flows, atmospheric chemistry, automotive catalysts, fuel science, and governmental regulations.