The aim of this study was to identify and quantify polyphenolic compounds in skin extracts from four Bulgarian grape varieties and compare them to those of seed extracts. The values of total phenolic contents, flavonoids, anthocyanins, procyanidins and an ascorbic acid in grape skin extracts were determined. The antioxidant capacities of skin extracts were evaluated using four different methods. The total phenolic content of skin extracts was 2–3 times lower than those of seed extracts. The significant difference between total parameter values of individual grape varieties were also found. According to the total phenolic content and antioxidant capacity of skin extracts, the different grape varieties were arranged in the following order: Marselan ≥ Pinot Noir ˃ Cabernet Sauvignon ˃ Tamyanka. The individual compounds in the grape skin extracts were determined using RP-HPLC and compared with those of the seed extracts. The determined composition of skin extracts was significantly different from the seed extracts’ composition. Quantitative evaluation of the procyanidins and catechins in the skins was carried out. A correlation between phenolic contents, individual compounds and antioxidant capacity of different extracts was found. The studied grape extracts have a potential to be applied as natural antioxidants in the pharmaceutical and food industries.