Apple fruit xyloglucan is predominantly built up from XXXG, XXFG, and XLFG units (G = beta-D-Glcp-, X = alpha-D-Xylp-(1-->6)-beta-D-Glcp-, L = beta-D-Galp-(1-->2)-alpha-D-Xylp-(1-->6)-beta-D-Glcp-, F = alpha-L-Fucp-(1-->2)-beta-D-Galp-(1-->2)-alpha-D-Xyl p-(1-->6)-beta-D-Glcp-). However, small amounts of oligosaccharides with a less heavily branched glucan backbone also occur. Structural analysis of two such oligosaccharides, isolated from a xyloglucan preparation digested with endoglucanase i.v., using a combination of FAB mass spectrometry and 1H NMR spectroscopy, afforded the identification of GFG and a dimer of GFG. The finding of the dodecasaccharide GFGGFG as a structural element of apple fruit xyloglucan is most unusual.