The consumption of red wine can provide substantial concentrations of antioxidant polyphenols, in particular grape anthocyanins (e.g., malvidin-3-O-β-D-glucoside (1)) and specific red wine pigments formed by reaction between anthocyanins and other wine components such as catechin (3), ethanol, and hydroxycinnamic acids. In this work, the antioxidant properties of red wine pigments (RWPs) are evaluated by the DPPH assay and by inhibition of the heme-induced peroxidation of linoleic acid in acidic conditions (a model of antioxidant action in the gastric compartment). RWPs having a 1 and 3 moieties linked via a CH3-CH bridge appear more potent than the pigment with a direct 1-3 linkage. Pyranoanthocyanins derived from 1 reduce more DPPH radicals than 1 irrespective of the substitution of their additional aromatic ring. Pyranoanthocyanins are also efficient inhibitors of the heme-induced lipid peroxidation, although the highly hydrophilic pigment derived from pyruvic acid appears less active