Total vaporization (TV) headspace (HS) gas chromatography (GC) is reported for the determination of ethanol in flavor oil microcapsules. Fifteen microliters of sample were placed in a headspace sample vial and a near-complete mass transfer of ethanol from the liquid phase to the vapor phase was obtained within one minute at 105 °C. This approach allowed the determination of ethanol in the sample by gas chromatography. Under the optimal conditions, the performance of this method was investigated, showing good linearity and a low limit of quantification equal to 8.95 mg/L. The relative standard deviation was less than 3.3%, and the recovery ranged from 95.4% to 101.3%. The method was efficient, accurate, and suitable for the quality control determination of ethanol in oil phase systems.