This paper describes the possibility of electronic nose-based detection and discrimination of volatile compound profiles of coffee from different countries roasted in a Gothot roaster under identical time and thermal regimes. The material used in the study was roasted Arabica coffee beans from Brazil, Ethiopia, Guatemala, Costa Rica, and Peru. The analyses were carried out with the use of the Agrinose electronic nose designed and constructed at the Institute of Agrophysics of the Polish Academy of Sciences in Lublin. The results of the volatile compound profile analysis provided by the Agrinose device were verified with the GC-MS technique. Chemometric tests demonstrated a dominant role of alcohols, acids, aldehydes, azines, and hydrazides in the coffee volatile compound profile. The differences in their content had an impact on the odor profile of the coffees originating from the different countries. High content of pyridine from the group of azines was detected in the coffee from Peru and Brazil despite the same roasting conditions. The results of the Agrinose analysis of volatile substances were consistent and correlated with the GC-MS results. This suggests that the Agrinose is a promising tool for selection of coffees based on their volatile compound profile.