The structures of six commercial hydrolyzable tannins, chestnut, oak, tara, sumach, chinese gall, and turkey gall tannins have been examined by matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry. Their oligomeric structures and structure distributions have been defined. Degradation products of rather different structure than what previously reported were present. Different galloyl glucose monomers were observed for chestnut and oak tannin extracts and in chinese gall gallotannin extract. Combination of positive- and negative-mode MALDI-TOF showed that most galloyl residues of the galloyl glucose chains were stripped from a skeletal glucose chain. Oligomers, in some cases up to 16 or 17 glucose units long, almost totally stripped of galloyl residues were observed. This indicated that a wide distribution up to very long galloylglucose chains exist in most commercial hydrolyzable tannin extracts. This indicated that these commercial tannin extracts are mainly composed of long galloyl glucose chains of mixed di-, tri-, and pentagalloyl glucose repeating units being present in the same chain. The presence of long glucose chains where most of the galloyl residues have been stripped indicates that their linkage may be Sugar residue to sugar residue. Commercial tara and turkey gall tannins have been shown to be mainly polygallic oligomers of up to eight gallic acid residues linked to each other in a chain. Commercial sumach extract revealed itself a more complex mixture of glucose oligomers up to 13 repeating units. (C) 2009 Wiley Periodicals, Inc, J Appl Polym Sci 113: 3847-3859, 2009