Structural diversity of pectins in açaí primary cell walls has been evaluated. A highly methoxylated homogalacturonan with a DM of 88% and Mw of 22 kDa was found. An AG-II with mainly 6-O- and 3,6-O-Galp units in the backbone was also isolated. This study brings new insights into the polysaccharide composition of palms primary cell walls.