Anthocyanin concentration and composition and the effect of steaming and baking on these were evaluated in tubers of Korean red-and purple-fleshed potato cultivars and breeding clones using liquid chromatography with diode array detection and electrospray ionization-mass spectrometry (LC-DAD-ESI-MS). Twenty-six anthocyanins were isolated, of which 24 were identified. Remarkably, five cis isomers were identified, of which four, viz., cis-petanin, cis-peonanin, petunidin 3-ciscaffeoylrutinoside-5-glucoside, and petunidin 3-cis-feruloylrutinoside-5-glucoside, are reported for the first time. Moreover, pelargonidin 3-p-coumaroylrutinoside-5-glucoside (pelanin), peonidin 3-p-coumaroylrutinoside-5-glucoside (peonanin) and petunidin 3-p-coumaroylrutinoside-5-glucoside (petanin) were identified as the principal anthocyanins. We found that the total anthocyanin content of coloured potatoes was decreased by steaming and baking compared with the raw state. In addition, we performed partial least square discriminant analysis (PLS-DA) to discriminate between the analyzed anthocyanins. Cis isomers seemed to play a vital role as a biomarker in the PLS-DA model based on the type of processing and colour of the tubers.