In some studies a relationship has been observed between increasing ethanol content in gasoline and increased particulate matter (PM) emissions from vehicles equipped with spark ignition engines. Ethanol features a greater enthalpy of vaporization (HOV) than gasoline and is commonly used in gasoline blends. In addition to increasing HOV, ethanol also influences vaporization by altering the liquid and vapor composition throughout the distillation process. A droplet vaporization model was developed to explore ethanol’s effect on the evaporation of aromatic compounds known to be PM precursors. The evolving droplet composition is being modeled as a distillation process, with non-ideal interactions between oxygenates and hydrocarbons accounted for using UNIFAC group contribution theory. Predicted composition and distillation curves were validated by experiments. Detailed hydrocarbon analysis was applied to fuel samples and to distillate fractions, and used as input for the initial droplet composition. With composition calculated throughout the distillation, the changing HOV and other physical properties can be found using reference data. The droplet can thus be modeled in terms of energy transfer, which in turn provides the transient mass transfer, droplet temperature, and droplet diameter. Model predictions suggest that non-ideal vapor-liquid equilibrium along with an increase in HOV can alter the droplet composition evolution. Results predict that the presence of ethanol causes enrichment of the higher boiling fractions (T90+) in the aromatic components as well as lengthens the droplet lifetime. A simulation of the evaporation process in a transient environment as experienced within a cylinder predicts a decrease in mixing time of the heaviest fractions of the fuel prior to spark initiation, possibly explaining observations linking ethanol to PM.