Relevant aspect of wine geographic origin is related to grapevine varieties used in specific wine country or region, and their secondary metabolites. Polyphenolic compounds, besides being important contributor to wine quality, are becoming more important as compounds having beneficial influence on human health. Volatile organic compounds have an important role in winemaking industry due to their contribution to wine sensory characteristics. The content and composition of secondary metabolites are influenced by many factors, among which is grape variety. The grapevine germplasm is highly variable and classified into geographic groups. These classifications were recently confirmed using genetic studies, and further classified varieties into genetic-geographic (GEN-GEO) groups. Thus, the aims of the research were to optimise the extraction method and analysis of free and bound volatile organic compounds from grapes by applying it in the analysis of mentioned compounds and to analyse polyphenolic profiles of grapevine varieties from different GEN-GEO groups. Furthermore, the aim was to determine the differences and single compounds that contribute to the differentiation of GEN-GEO groups. Before analysing volatile organic compounds, it was necessary to optimise solid-phase microextraction (SPME)-Arrow conditions. SPME-Arrow is a new extraction technique recently employed in the analysis of volatiles in food matrices. Regarding grape and wine volatiles the published work is scarce. Thus, the aim was to develop and validate SPME-Arrow extraction technique coupled with GC/MS instrument. To optimise SPME-Arrow extraction conditions, Box-Behnken experimental design and response surface methodology were used. Extraction conditions that were optimised were extraction temperature, incubation time, exposure time, and desorption time. Analysed volatile organic compounds were free forms directly from grape skins, and bound forms released from grape skins after acid hydrolysis. Before starting the optimization process, some preliminary experiments using one-factor-at-the-time methodology were necessary for determination of sample weight, injection mode, and SPME-Arrow coating. These parameters have an important influence on the extraction efficiency, and the best results gave 100 mg sample weight, splitless injection mode, and DVB/CWR/PDMS fibre. After performing the experiments generated by experimental design, the results showed that the most significant factors were extraction temperature and exposure time for both free and bound volatiles. For both factors, an increase in their values positively affected the extraction efficiency for almost all classes of volatile compounds. For free volatile compound the optimum extraction conditions are: extraction temperature 60°C, incubation time 20 min, exposure time 49 min, and desorption time 7 min. The optimum conditions for bound volatile compounds are: extraction temperature 60°C, incubation time 20 min, exposure time 60 min, and desorption time 7 min. After optimization process, the polyphenolic and volatile organic compounds were analysed in 50 grapevine varieties from three GEN-GEO groups, that is from five countries. Groups included in this research are C2 (varieties from Italy and France), C7 (varieties from Croatia), and C8 (varieties from Spain and Portugal). The polyphenolic compounds were analysed by HPLC, while volatile organic compounds were analysed using the optimised SPME-Arrow method. Discriminant analysis was used to determine the differences between groups and to define the contribution of individual compounds in the discrimination. Polyphenolic compounds analysed belonged to the classes of anthocyanins, flavan-3-ols, flavonols, phenolic acids, and stilbenes, while volatile compounds belonged to the classes of aldehydes, ketones, acids, alcohols, monoterpenes, sesquiterpenes, esters. Among these classes the most abundant for polyphenols were anthocyanins, flavan-3-ols, and flavonols, while the most abundant volatiles belonged to aldehydes and alcohols. The polyphenolic and volatile profiles differed among grapevine varieties, as well as GEN-GEO groups. The discriminant analysis clearly separated groups based on their polyphenolic and volatile profiles, with all classes of compounds contributing to the discrimination. Some of the compounds contributing to the differentiation of groups were found in relatively small quantities. It can be concluded that discrimination of different GEN-GEO groups is more influenced by the differences in the content of numerous analysed polyphenolic and volatile organic compounds, and less influenced by the composition of compounds within the classes of secondary metabolites.