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Ethanol is a promising alternative to fossil fuels because it can be produced from biomass resources that are renewable. Due to the amount of production, however, the usage would be limited to blends with other conventional fuels. Ethanol-fuel blends are azeotropic and have unique vaporization characteristics different from blends composed of aliphatic hydrocarbons, so that the present study developed a numerical scheme which takes into account the vapor-liquid equilibrium of azeotrope in order to update the author's original version of the multi-component fuel CFD model and to evaluate the effect of mixing ethanol into gasoline on the evaporation process. The numerical simulation was implemented for evaporating sprays of ethanol-n-heptane blends, which are injected through a single hole nozzle. In addition to the vapor-liquid equilibrium, the effect of the latent heat of vaporization was investigated.