Anthocyanins, present in the berries of Smilax aspera L., a creeping shrub typical of the Mediterranean region, were extracted and identified for the first time. The pigments were extracted from the skin of the berries with of 0.1% HCl in methanol solution, purified on a C-18 solid-phase cartridge and characterized by means of HPLC-DAD-MS analysis. From spectral analysis before and after acid and alkaline hydrolysis, it was noted that pelargonidin 3-O-rutinoside represented about 83% of the total anthocyanin content in the skin of Smilax aspera berries. A low quantity of cyanidin 3-O-rutinoside (13%) was also found. The attractive colour and the great abundance of the plant in the south of Italy make Smilax aspera berries a new and very good source of natural pigments.