The oxidation processes of unsaturated fatty acid methyl esters (FAMEs) and vegetable oils with molecular oxygen, proceeding through a radical mechanism, lead to the formation of a wide range of compounds. The primary oxidation products, hydroperoxides, undergo further decomposition to form products with a lower molecular weight or participate in cross‐linking reactions leading to the accumulation of products with a higher molecular weight than the raw material. A number of researches note an increase concentration of oligomeric products and esters during the oxidation of FAME. The study of literary sources made it possible to establish that the accumulation of these substances correlates with each other. The mechanisms of ester formation described in the literature suggest the direct participation of either acids or hydroperoxides in these reactions. The work examines the main ways of accumulation of heavy products and “new” esters during the oxidation of FAMEs.