The aim of this study was to identify chemical markers of commercial tropical red wines with the potential to apply for the Geographical Indication-GI São Francisco Valley. Volatile organic compounds of nine different commercial red wines from the São Francisco Valley, located in the Caatinga region of Brazil, that meet the classic oenological parameters for commercialization, were extracted and separated by the HS-SPME/GC-MS technique, and identified. A total of 103 volatile compounds were identified and classified into 13 chemical groups, of which the esters and alcohols were the majority groups. Similarities were found in the composition of 27 compounds identified in all wines; however, the cultivars influenced the distinction of volatiles expressed exclusively in only one type of wine. Among these, 22 compounds were highlighted for having been identified for the first time in wines, such as 3-phenyl-undecane and 4-phenyl-decane. These exclusive compounds are possible markers which confirm the typicality of tropical red wines of this region, and can contribute to the qualitative description and enhancement of regional identity for wines from the São Francisco Valley.