Cell walls were prepared from apple parenchyma by a phenol:buffer procedure. Polyphenols were extracted from freeze-dried apple parenchyma by methanol and water:acetone, and purified by preparative HPLC. Interactions were quantified by bringing into contact suspended cell walls and polyphenol solutions. Hydroxycinnamic acids and (-)-epicatechin did not bind to cell walls. Binding of procyanidins was fast and reached up to 0.6 g per g cell walls. The amounts of procyanidins bound increased with the initial concentration and with DPn. Procyanidins could be partially desorbed by buffer, more being desorbed in the presence of dissolved cell wall polysaccharides. They were totally desorbed using 8 M urea or acetone:water. Higher polymers were bound selectively from procyanidin mixtures, and very high average DPn were obtained in extensively washed complexes. Binding of procyanidins inhibited enzymic degradation of the cell walls.