During the last decade anthocyanin-related research has been intensified due to the fact that a high intake of anthocyanin-rich food has been linked to health-protecting effects. Pigmented potato (Solanum tuberosum L.) varieties constitute an important source of anthocyanins. So far, little information concerning the metabolism, bioactivity, and bioavailability of acylated anthocyanins has been published because it is still difficult to obtain pure pigments on a preparative scale. In our studies, the pigment composition of the blue-fleshed potato cultivars 'Hermanns Blaue', 'Vitelotte', 'Shetland Black', and 'Valfi' were examined. The preparative isolation of anthocyanins was carried out by applying two different methods of countercurrent chromatography (CCC), the so-called High-Speed Countercurrent Chromatography (HSCCC) and Low Speed Rotary Countercurrent Chromatography (LSRCCC), respectively. By application of LSRCCC, HSCCC, as well as preparative HPLC it was possible to isolate and characterize the major pigments, i.e. 3-p-coumaroylrutinoside-5-glucosides of petunidin, malvidin, and peonidin, of the four cultivars. From the cultivar 'Hermanns Blaue' LSRCCC enabled the isolation of the major pigment petunidin-3-p-coumaroylrutinoside-5-glucoside on a preparative scale. Furthermore, it was possible to separate and characterize several non-acylated 3,5-diglucosides, i.e. 3-rutinoside-5-glucosides of petunidin and malvidin, acylated 3,5-diglucosides, i.e. 3-feruloylrutinoside-5-glucosides of petunidin and malvidin as well as the 3-caffeoylrutinoside-5-glucoside of petunidin, and the p-coumaric acid derivative petunidin-3-p-coumaroylrutinoside. Purity and identity of the so-obtained anthocyanins were controlled by HPLC-DAD, ESI-MS n , and NMR-measurements.