Grape volatile organic compounds (VOCs) play an important role in the winemaking industry due to their contribution to wine sensory characteristics. Another important role in the winemaking industry have the grapevine varieties used in specific regions or countries for wine production. Due to the high variability of grapevine germplasm, grapevine varieties are as classified based on their genetic and geographical origin into genetic-geographic groups (GEN-GEO). The aim of this research was to investigate VOCs in 50 red grapevine varieties belonging to different GEN-GEO groups. The study included varieties from groups C2 (Italy and France), C7 (Croatia), and C8 (Spain and Portugal). The analysis of VOCs was performed by SPME-Arrow-GC/MS directly from grape skins. The analyzed VOCs included aldehydes, ketones, acids, alcohols, monoterpenes, and sesquiterpenes. The most abundant VOCs were aldehydes and alcohols, while the most numerous were sesquiterpenes. The most abundant compounds, aldehydes and alcohols, were found to be (E)-2-hexenal, hexenal, (E)-2-hexen-1-ol, and 1-hexanol. Using discriminant analysis, the GEN-GEO groups were separated based on their volatile profile. Some of the individual compounds contributing to the discrimination were found in relatively small amounts, such as benzoic acid, (E,E)-2,4-hexadienal, 4-pentenal, and nonanoic acid. The groups were also discriminated by their overall volatile profile: group C2 was characterized by a higher content of aldehydes and alcohols, and group C8 was characterized by a higher content of sesquiterpenes and acids. Group C7 was characterized by all low amount of all classes of VOCs.