The utility of electrospray and tandem mass spectroscopy (ES-MS and MS- MS) in anthocyanin characterization was tested using different anthocyanin extracts. Anthocyanins were semipurified by using a C-18 resin, washed with acidified water followed by ethyl acetate, and recovered with acidified methanol. Samples were directly injected into a mass spectrometer in either aqueous or methanolic solutions. The positive charge of anthocyanins favored fast and effective ES-MS detection of intact molecular ions. Little interference from other compounds was observed when the ethyl acetate cleaning procedure was used. Tandem mass spectroscopy provided clear and characteristic fragmentation patterns. The voltage used affected only the proportions at which these fragments were present. ES-MS may be used as a fast procedure for identification of anthocyanins, requiring minimal sample preparation. In combination with HPLC, ES-MS and MS-MS could be very powerful tools for anthocyanin characterization and monitoring the authenticity of anthocyanin-containing fruit juices and vegetable extracts.