Several oligosaccharide fragments, ranging from 2 to 9 contiguous residues, have been isolated from purified tamarind xyloglucan using enzymatic digestion and partial acid hydrolysis. Structures were determined using matrix assisted laser adsorption ionization-time of flight (MALDI-TOF) mass spectrometry, gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), and Dionex high pH anion exchange-high performance liquid chromatography (HPAE-HPLC). These fragments will be used to identify reaction products from xyloglucan xylosyltransferase and glucosyltransferase enzyme assays and as possible acceptor molecules for these enzymes.