An LC-PDA-ESI/MS(n) profiling method was used to identify the anthocyanins of purple Bordeaux radish and led to the assignment of 60 anthocyanins: 14 acylated cyanidin 3-(glucosylacyl)acylsophoroside-5-diglucosides, 24 acylated cyanidin 3-sophoroside-5-diglucosides, and 22 acylated cyanidin 3-sophoroside-5-glucosides. The identifications were supported by the presence of 3-sophoroside-5-diglucoside and 3-sophroside-5-glucoside of cyanidin in the alkaline-hydrolyzed extract. A reliable method to identify the anthocyanins containing 3-(glucosylacyl)acylsophorosyl functions is described. The tentative identifications were obtained from tandem mass data analysis and confirmed by high-resolution mass measurements. Further assignments were made for some anthocyanins from a comparison of the mass and UV-vis data and elution order with those of the anthocyanins in the authors' polyphenol database and from consideration of the structural characteristics of the anthocyanins from similar plants and similar anthocyanins in the literature. The presence of 38 acylated cyanidin 3-sophoroside-5-diglucosides and around 10 acylated cyanidin 3-sophoroside-5-malonylglucosides in plants is reported here for the first time.