Anthocyanins are polyphenolic pigments responsible for most of the color diversity found in plants. Here the in vivo color expression and the stability of anthocyanins are interpreted by extrapolation of the results acquired in vitro with model solutions of pigments obtained through plant extraction or laboratorial synthesis. Behavior of anthocyanins is explained in terms of molecular interactions of the chromophore units with parts of the pigments themselves and/or with some constituents of the plant cell. These include, among others, diverse polyphenols, metal cations, and inorganic salts. Attention is also given to the biophysicochemical environment found in plant vacuoles that plays a fundamental role on the intermolecular and intramolecular associations displayed by anthocyanins. For example, anthocyanin Z-chalcones (retrochalcones) provide an unexpected open cavity for the ferric cation. Medicinal, nutritional, and industrial applications of anthocyanins are proposed.Colors are conferred to plants by chlorophylls, carotenoids, and fl avonoids (Britton, 1983). Chlorophylls are responsible for the green colors displayed by the leaves, whereas carotenoids provide some of the red-orange hues often found in fruits, fl owers, and other plant constituents. Flavonoids belong to a larger family, the polyphenols, and can be found in most fl owers and fruits (Brouillard & Dangles, 1993;Andersen & Jordheim, 2006). They include the principal elements responsible for the color diversity found in the plant world, the anthocyanins (Fig. 1.1). In fact, these pigments are the only polyphenols that possess the ability to absorb light both in the ultra-violet and in all the visible range (from yellow-orange to bluish-green) (Goto & Kondo, 1991). It is well known that anthocyanins are at the origin of plants' most brilliant colors, a phenomenon particularly visible from fl owers. Nevertheless, there exists only one chromophore -the fl avylium nucleus -whose subtle interactions with vacuole biochemicals, including water, are capable of providing all kind of colors.Anthocyanins are stored in an organized aqueous medium in the cell vacuoles. A slightly acidic environment (pH 3-5;Stewart et al., 1975) rich in inorganic ions and other polyphenols is essential for the transformations in these pigments that enable the formation of molecular complexes and subsequent color changes and stabilization (Brouillard & Dangles, 1993).