A series of condensed tannin derivatives with non-, mono-, di- and tri-hydroxylated B-rings were synthesized starting from phloroglucinol and benzaldehyde derivatives. The protein-precipitating capacity of these condensed tannin derivatives showed 1) A condensed tannin with only a 4′-hydroxylated B-ring has almost the same protein-precipitating capacity as that of a condensed tannin with 3′,4′-dihydroxylated or 3′,4′,5′-trihydroxylated B-rings. 2) The complexing ability of phenolic hydroxyl groups in the B-ring are effective in the order ofp- >m- >o-positions.