The association of automotive fuel composition with exhaust reactivity was studied in an experimental program that involved testing with different automotive engines and with gasolines of varied composition. Results showed clearly the exhaust reactivity to increase with increasing levels of polyalkylbenzenes in the fuel. No other systematic patterns of high significance were detected in the association of exhaust reactivity with several broadly defined groups of fuel components. For the purpose of this study, had it been possible, fuel composition should have been defined and expressed in terms of component groups such that the potential for exhaust reactivity would be the same within each group and different from group to group. Classification of fuel components in terms of the paraffins-olefins-aromatics groups does not meet the latter requirements. For appropriate classification of fuel components more information is needed on the combustion of hydrocarbons in the multicylinder internal combustion engine. Statistical analysis of the mass emissions data showed significant car and fuel effects on hydrocarbon, carbon monoxide, nitric oxide, total aldehydes, and formaldehyde emission levels and on total photochemical reactivity. Car-fuel interactions were not significant at the 90-pct level. Correlations were found between mass emission parameters and fuel composition.