This is the first in a series of papers dealing with the structure of cell walls isolated from suspension-cultured sycamore cells (Acer pseudoplatanus) . These studies have been made possible by the availability of purified hydrolytic enzymes and by recent improvements in the techniques of methylation analysis. These techniques have permitted us to identify and quantitate the macromolecular components of sycamore cell walls. These walls are composed of 10% arabinan, 2% 3,6-linked arabinogalactan, 23% cellulose, 9 % oligo-arabinosides (attached to hydroxyproline), 8% 4-linked galactan, 10% hydroxyproline-rich protein, 16 % rhamnogalacturonan, and 21% xyloglucan.The structures of the pectic polymers (the neutral arabinan, the neutral galactan, and the acidic rhamnogalacturonan) were obtained, in part, by methylation analysis of fragments of these polymers which were released from the sycamore walls by the action of a highly purified endopolygalacturonase. The data suggest a branched arabinan and a linear 4-linked galactan occurring as side chains on the rhamnogalacturonan. Small amounts or pieces of a xyloglucan, the wall hemicellulose, appear to be covalently linked to some of the galactan chains. Thus, the galactan appears to serve as a bridge between the xyloglucan and rhamnogalacturonan components of the wall.The rhamnogalacturonan consists of an a-(1 -; 4)-linked galacturonan chain which is interspersed with 2-linked rham. nosyl residues. The rhamnosyl residues are not randomly distributed in the chain but probably occur in units of rhamnosyl-(1 -4 4)-galacturonosyl-(1 -e 2)-rhamnosyl. This sequence appears to alternate with a homogalacturonan sequence containing approximately 8 residues of 4-linked galacturonic acid. About half of the rhamnosyl residues are branched, having a substituent attached to carbon 4. This is likely to be the site of attachment of the 4-linked galactan.The hydroxyprolyl oligo-arabinosides of the hydroxyproline. rich glycoprotein contain 3-linked, 2-linked, and terminal arabinosyl residues. The structure of the hydroxyprolyl oligoarabinosides deduced from our methylation studies agrees with the structure reported for similar oligosaccharides. Cellulose, hemicellulose, pectic polysaccharide, structural protein, and lignin have been identified as the major components of the plant cell wall. These components have been discussed in several recent reviews (4,9,26,35,47,52,63,64,68). Lignin is a characteristic component of secondary walls and is therefore not further discussed.Crystalline cellulose fibers make up an important part of the framework of the cell walls of all higher plants. Electron microscopy and x-ray diffraction have led to a rather detailed description of the structure of this wall component (35,57,69