Anthocyanins are water-soluble pigments found in the cell vacuoles of fruits and flowers, performing several roles from insects attraction to stress protection. Their antioxidant activity contributes to human health, and consuming plant-derived products provides their higher source in the diet. Although their colour and nutritional features, their contribution to sensory properties of foods has not been widely investigated. In wine, preferences are connected with sensory attributes of colour, aroma, taste, and mouthfeel. In this study, grape anthocyanin extracts (TAE) were fractionated using centrifugal partition chromatography (CPC) and preparative HPLC in three fractions, i.e glucoside (GF), acetylated (AF) and cinnamoylated (CF) anthocyanins. Sensory properties were investigated by chemical analysis, as reactivity towards bovin serum albumin (BSA) and salivary proteins, and in tasting sessions to assess anthocyanins best estimated thresholds (BET) in wine-like solution. Anthocyanins reacted with both BSA and salivary proteins, but to different extents, because higher interaction between salivary proteins and anthocyanins were found. Cinnamoylated anthocyanins are the most reactive to salivary proteins. Tasting sessions suggested an involvement of anthocyanins as in-mouth contributors in wine, since their BETs were 255, 297, 68, and 58 mg/L for TAE, GF, AF, and CF, respectively, and the descriptors reported were astringency and bitterness.