1. 2-Hydroxyphenylacetic acid, a natural phenolic product found in the genus Astilbe, derives from the shikimic acid pathway via phenylpyruvic acid. The existence of two routes for the biosynthesis of 2-hydroxyphenylacetic acid could be demonstrated : a ) A direct transformation of phenylpyruvic acid into 2-hydroxyphenylacetic acid involving a migration of the side chain. More than 95 O l 0 of the tritium activity of 2-hydroxyphenylacetic acid was localized in position 5 when ~-[4-~H]phenylalanine was fed. This complex oxidation is analogous to the known conversion of 4-hydroxyphenylpyruvic acid to homogentisic acid. b) A hydroxylation of [4-3H]phenylacetic acid t o [4-3H]2-hydroxyphenylacetic acid was observed in vivo, and was also found to take place in vitro utilizing the system peroxidaseendiol-0,.2 . 2,3-Dihydroxyphenylacetic acid and 2-hydroxy-3-methoxyphenylacetic acid could be established as natural products occurring in higher plants. Their chemical synthesis is described. By feeding experiments the following metabolic pathway is suggested : 2-hydroxyphenylacetic acid --f 2,3-dihydroxyphenylacetic acid --f 2-hydroxy-3-methoxyphenylacetic acid. 3,4-Dihydroxyphenylacetic acid and 3-methoxy-4-hydroxyphenylacetic acid have been detected in extracts from various species of Astilbe and identified by paper chromatography. These two acids are metabolic products of 4-hydroxyphenylacetic acid.3. Experiments with [U-14C]shikimic acid and ~~-[~t -~~c ] p h e n y l a l a n h e seem to indicate that the regulation of the biosynthesis of 2-hydroxyphenylacetic acid and 4-hydroxyphenylacetic acid takes place on the level of prephenic acid.4. Preliminary results were obtained consistent with the hypothesis that in Astilbe chinensis the 2,3-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid and 2,5-dihydroxyphenylacetic acid are further metabolized and can be degraded by ring cleavage.