The hot water soluble green coffee arabinogalactans, representing nearly 7% of total coffee bean arabinogalactans, were characterized by 1 H and 13 C NMR and, after partial acid hydrolysis, by ESI-MS/MS. Data obtained showed that these are highly branched type II arabinogalactans covalently linked to proteins (AGP), with a protein moiety containing 10% of 4-hydroxyproline residues. They possess a β-(1→3)-Galp/β-(1→3,6)-Galp ratio of 0.80, with a sugars composition of Rha:Ara:Gal of 0.25:1.0:1.5, and containing 2mol% of glucuronic acid residues. Beyond the occurrence of single α-l-Araf residues and [α-l-Araf-(1→5)-α-l-Araf-(1→] disaccharide residues as side chains, these AGPs contain unusual side chains at O-3 position of the β-(1→6)-linked galactopyranosyl residues composed by [α-l-Rhap-(1→5)-α-l-Araf-(1→] and [α-l-Rhap-(1→5)-α-l-Araf-(1→5)-α-l-Araf-(1→] oligosaccharides. Rhamnoarabinosyl and rhamnoarabinoarabinosyl side chains are reported for the first time as structural features of plant arabinogalactan-proteins.