The structures of hydrolysable tannins, each existing as an equilibrium mixture due to tautomerization at the sugar core(s) or at the dehydrohexahydroxydiphenoyl group (five- and six-membered hemiacetal forms) in the molecule, were elucidated by NMR, employing 2D NMR techniques (COSY, NOESY, H-1-C-13 long-range COSY, etc.), on derivatives which avoid the spectral complication due to equilibration.