During processing of plant-based foods, cell wall polysaccharides and polyphenols, such as procyanidins, interactextensively, thereby affecting their physicochemical properties along with their potential health effects.Although hemicelluloses are second only to pectins in affinity for procyanidins in cell walls, a detailed study oftheir interactions lacks. We investigated the interactions between representative xylose-containing water-solublehemicelluloses and procyanidins. Turbidity, ITC and DLS were used to determine the relative affinities, andtheoretical calculations further ascertained the interactions mechanisms. Xyloglucan and xylan exhibitedrespectively the strongest and weakest interactions with procyanidins. The different arabinoxylans interactedwith procyanidins in a similar strength, intermediate between xyloglucans and xylans. Therefore, the strength ofthe interaction depended on the structure itself rather than on some incidental properties, e.g., viscosity andmolar mass. The arabinose side-chain of arabinoxylan did not inhibit interactions. The computational investi-gation corroborated the experimental results in that the region of interaction between xyloglucan and procya-nidins was significantly wider than that of other hemicelluloses.