Varietal volatile compounds are characteristic of each variety of grapes and come from the skins of the grapes. This work focuses on the development of a methodology for the analysis of free compounds in grapes from Trincadeira, Cabernet Sauvignon, Syrah, Castelão and Tinta Barroca from the 2021 and 2022 harvests, using HS-SPME-GC × GC-TOFMS. To achieve this purpose, a previous optimization step of sample preparation was implemented, with the optimized conditions being 4 g of grapes, 2 g of NaCl, and 2 mL of HO. The extraction conditions were also optimized, and it was observed that performing the extraction for 40 min at 60 °C was the best for identifying more varietal compounds. The fiber used was a triple fiber of carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS). In addition to the sample preparation, the analytical conditions were also optimized, enabling the adequate separation of analytes. Using the optimized methodology, it was possible to identify fifty-two free volatile compounds, including seventeen monoterpenes, twenty-eight sesquiterpenes, and seven C-norisoprenoids. It was observed that in 2021, more free varietal volatile compounds were identifiable compared to 2022. According to the results obtained through a linear discriminant analysis (LDA), the differences in volatile varietal signature are observed both among different grape varieties and across different years.