The purpose of this paper is to review current studies concerning the relationship of fuel composition to vehicle engine-out and tail-pipe emissions and to outline future research needed in this area. A number of recent combustion experiments and vehicle studies demonstrated that reformulated gasoline can reduce vehicle engine-out, tail-pipe, running-loss, and evaporative emissions. Some of these studies were extended to understand the fundamental relationships between fuel composition and emissions. To further establish these relationships, it was necessary to develop advanced analytical methods for the qualitative and quantitative analysis of hydrocarbons in fuels and vehicle emissions. The development of real-time techniques such as Fourier transform infrared spectroscopy, laser diode spectroscopy, and atmospheric pressure ionization mass spectrometry were useful in studying the transient behavior of exhaust emissions under various engine operating conditions. Laboratory studies using specific fuels and fuel blends were carried out using pulse flame combustors, single- and multicylinder engines, and vehicle fleets. Chemometric statistical methods were used to analyze the large volumes of emissions data generated from these studies. Models were developed that were able to accurately predict tail-pipe emissions from fuel chemical and physical compositional data. Some of the primary fuel precursors for benzene, 1,3-butadiene, formaldehyde, acetaldehyde and C2-C4 alkene emissions are described. These studies demonstrated that there is a strong relationship between gasoline composition and tail-pipe emissions.