Although much has been learned in recent years about the atmospheric reactivity of the hydrocarbon (HC) emissions from gasoline-fueled vehicles, there is only a limited database of corresponding information for exhaust emissions from diesel-fueled vehicles. An assessment of exhaust reactivity requires “speciation”, or measurement of the individual species of the HC fraction. The HC exhaust emissions are a complex mixture of unburned and partially burned fuel components. Because diesel fuel contains a much higher molecular weight range (typically C9-C26) than gasoline (typically C5-C12), new methodology was required to accommodate the collection and analysis of the >C12 fraction of the HC exhaust. As part of a study of the effects of fuel and other factors on the chemical nature of diesel emissions, we have developed a method for the collection and analysis of the semivolatile or heavy HC (>C12) fraction of the exhaust. The method has a sensitivity for individual HC species of 0.2 ng/L of dilute exhaust. In this report we describe the method and its application to fuel and exhaust analysis. Speciation results are presented for two fuels and for the heavy hydrocarbon fraction of the exhaust from selected vehicle tests.