The objective of this research was to employ headspace solid-phase microextraction (HS-SPME) and gas chromatography mass spectrometry (GC-MS) to characterize the volatile fraction of three varieties of coffee produced in Brazil: bourbon amarelo (C. arabica), robusta (C. robusta) and catuai vermelho (C. arabica). The beverages were brewed by percolation (55 g of coffee powder and 1000 mL of distilled water at 90 °C), follow the instructions of the Specialty Coffee Association of America. We tested the extraction efficiency of five different SPME commercial fiber coating. For the SPME fiber that showed the best extraction efficiency, the extraction time, temperature and amount of NaCl parameters were optimized using response surface methodology. Once the optimal extraction conditions were known (DVB/CAR/PDMS fiber, 60 °C for extraction temperature, 25 min for extraction time, and 3 g of sodium chloride), the volatiles of the coffee were extracted and analyzed by GC-MS. The bourbon amarelo coffee presented the highest area values for 2,4,5-trimethylthiazole (chocolate, nut and coffee aroma), followed by 2-ethyl-3,5-dimethylpyrazine (roasted peanut, nuts, caramel, coffee, mold and cocoa) and guaiacol (smoke, spice, medicinal and vanilla). Robusta coffee also show 2,4,5-trimethylthiazole (chocolate, nut and coffee aroma), followed by 2-methoxy-4-vinylphenol (roasted peanut, cedar, amber and fresh wood) and 2-ethyl-3,5-dimethylpyrazine (roasted peanuts, nuts, caramel, coffee, mold and cocoa). While the catuai vermelho coffee presented the major compound 2-methoxy-4-vinylphenol (roasted peanut, cedar, amber and fresh wood flavor), followed by 2,4,5-trimethylthiazole (chocolate, nut and coffee) and 2-ethyl-3,5-dimethylpyrazine (roasted peanuts, nuts, caramel, coffee, mold and cocoa). This research strategy combined the advantages of a detailed chemical profile of volatile components present in the coffees that can be correlated in the future, by the use of chemometric tools, with the results of Descriptive Sensory Analysis, to know the relationship between the volatile composition of the coffees and the sensorial profile.