An HPLC/MS application to anthocyanic compounds of Vitis vinifera L. is described. A series of liquid-liquid and liquid-solid extractions yielded an extract containing anthocyanic compounds only. This extract was analyzed by HPLC/DAD and HPLC/MS, and UV-vis and MS spectra of each compound were obtained. An API ion-spray interface allowed coupling between the chromatographic system and a mass spectrometer. This interface allowed application of the chromatographic conditions normally used in the HPLC analysis of anthocyanic compounds, which led to the identification of the 3-glucosides, the 3-acetylglucosides, and the 3-p-coumaroylglucosides of delphinidin, cyanidin, petunidin, peonidin, and malvidin, already known in the literature. Two 3-caffeoylglucoside derivatives were identified too, and it has been possible to identify, for the first time, some 3,5-diglucosides that are known to be present in Vitis sp. but not in Vitis vinifera L. The investigated cultivars showed the same anthocyanic profile but dramatic quantitative differences