The method described in literature for alkylating 3-hydroxy-ϒ-pyrone (pyromeconic acid) at the 2-position consists of the reduction of the hydroxylic intermediates or the Mannich base which were derived from the reaction with aldehydes. The application of this method is limited, for example, the introduction of isopropyl or phenyl groups by this means is impossible. The present authors have developed a novel method for direct alkylation of pyromeconic acid at the 2-position by refluxing the glacial acetic acid solution of pyromeconic acid in the presence of diacyl peroxides or aroyl peroxides. A radical mechanism seems to be operative in the present reaction.