The structure of an arabinogalactan-protein (AGP) isolated from grape juice was studied by methylation analysis, n.m.r. spectroscopy, and interaction with peanut lectin, after specific degradation with purified enzymes and/or Smith degradation. AGP appeared to be homogeneous with a weight-average molecular weight of 110 000. Treatment of AGP with arabinofuranosidase released 88% of the arabinose and left GP1. Hydrolysis of GP1 with an endo-(1 --> 6)-beta-D-galactanase removed 50% of the galactose and left GP2. Smith degradation of GP1 gave a 3-linked galactan that still contained 3,6-linked residues. Endogalactanase- and Smith-degraded GP1, but not AGP and GP1, reacted strongly with peanut lectin. Thus, AGP is a 3-linked galactan cross-linked at positions 6. The core also carries, at positions 6,6-linked galactan chains heavily 3-substituted with arabinofuranose residues.