Elucidation of the main structural unit of a water-soluble, high-molecular weight preparation from the crude polysaccharides of Anchusa italica Retz. roots has been carried out. According to ¹³C NMR, ¹H NMR and 2D heteronuclear ¹H/¹³C HSQC spectral data, the main structural element of the high-molecular, water-soluble preparation was a regularly substituted polyoxyethylene chain, namely poly[oxy-1-carboxy-2-(3,4-dihydroxyphenyl)ethylene]. Most carboxylic groups of this caffeic acid-derived polymer of A. italica are methylated.