Cold extraction methods with ethanol applied to the flavedo of Citrus fruits have been commonly applied for the preparation of several liquors. In order to obtain the extraction optimization and then the best ratio of functional ingredients in the extract, the flavedo of Citrus grandis Osbeck (pummelo) was subjected to a maceration with absolute ethanol at room temperature as well as at 40 °C. The kinetics of the extraction methods were monitored by UV–VIS spectroscopy, and a chemical fingerprint characteristic of each extract was determined by statistical multivariate analysis of the UV–VIS raw data. Additionally, the extracts were qualitatively characterized by NMR spectroscopy as well as by solid phase micro extraction followed by gas chromatography/mass spectrometry (GC/MS). NMR analysis confirmed the presence of the typical flavanones of Citrus such as naringin and naringenin, while the GC/MS analysis showed that the headspace of the liquor is characterized by two main compounds represented by β-myrcene and limonene. At the end, the temperature seems to not affect the time of extraction, which is complete after 25 h; however, UV–VIS-based multivariate analysis revealed that a different overall chemical composition is obtained depending on the temperature, probably due to the extraction of minor chemicals as well as due to different levels of the same compounds in the two extracts.