The effect of ambient temperature and relative humidity on the dynamics of ethanol drop evaporation is investigated. Although drop evaporation of mixtures and pure fluids has been extensively studied, very little is known about the transition from a pure fluid to a binary mixture following transfer of a second component present in the atmosphere. This is of importance for industrial, biological and medical applications where the purity of the solvent is paramount. Adsorption–absorption and/or condensation of water into ethanol drops during evaporation is presented through direct quantification of the drop composition in time. In particular, we combine drop profile measurements with Gas Injection Chromatography (GIC) to directly quantify the amount of ethanol evaporated and that of water intake over time. As expected, drops evaporate faster at higher temperatures since both the ethanol saturation concentration and the vapor diffusion coefficient are directly proportional to temperature. On the other hand, increases in the ethanol evaporation rate and in the water intake are observed at higher relative humidity. The increase in ethanol evaporation at higher relative humidity is interpreted by the greater diffusion coefficient of ethanol into humid air when compared to dry air. Moreover, as ethanol evaporates in a high humidity environment, the drop interfacial temperature falls below the dew point due to evaporative cooling and water condenses compared to lower humidity conditions. As a consequence of the heat released by adsorption–absorption and/or condensation, a greater temperature is reported at the liquid–vapor interface as confirmed by IR thermography, inducing a greater ethanol saturation concentration at the surface and hence a greater driving force for evaporation. By coupling the drop profile and the composition of ethanol and water within the drop, we propose a combined evaporation–adsorption/absorption and/or condensation empirical correlation. The proposed correlation accounts for: the decreases in ethanol concentration due to water adsorption–absorption and/or condensation, the diffusion coefficient dependence on relative humidity, and the amount of water intake during evaporation. The proposed empirical correlation agrees remarkably well with experimental observations.