Τhe polyclonality of a grapevine cultivar plays a significant role in the quality of the viticultural products it yields, especially when age-old grapevine cultivars such as Korinthiaki Staphis are entailed. The aim of the present study was to determine the polyphenol content and antioxidant capacity of the berry skins of seven (7) biotypes-possibly clones of the grapevine cultivar Korinthiaki Staphis (Vitis vinifera L.). For the purposes of the present study, it is worth noting at this point that all seven biotypes had been cultivated in the same geographic location and under the same climate and soil conditions. In view of the study's aim, the biotypes were studied using high performance liquid chromatography (HPLC) coupled with a diode array detector and spectrophotometer. The results revealed that the levels of both polyphenol content and antioxidant capacity were high in all biotypes. Statistically significant differences between and among the biotypes were duly recorded: (a) Biotype KS15 exhibited a high concentration in total anthocyanins, total flavanols, total flavonoids, acidity, and total soluble solids; (b) biotype KS6 exhibited a high concentration in total soluble solids, total flavanols, epicatechin, procyanidins B1 and B2, trans-resveratrol, and piceid; and (c) biotype KS1 exhibited a high concentration in quercetin, rutin, catechin, epicatechin, trans-resveratrol, and piceid; and the highest concentration in the phenolic aldehyde vanillin. Both polyphenolic content and antioxidant capacity are biotype-dependent. Thus, when striving for products of exceptional quality it is crucial for viticulturists to exploit the appropriate biotypes of Korinthiaki Staphis. Research and results on the studied biotypes suggest that KS15, KS1, and KS6, individually or in combination, are the most suitable ones for the establishment of productive vineyards.