Tannic acid, a polyphenol of natural origin, assembled in alternation with polyelectrolytes via the layer-by-layer method retains its ability to scavenge free radicals. Kinetics of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation-radical bleaching by tannic acid/polyelectrolyte films depend on multilayer architecture, while total radical scavenging capacity depends on the amount of adsorbed TA.