Wood is a formidable composite material with unique biological functions (as secondary plant cell wall) and outstanding properties to be exploited in material applications. Hemicelluloses act as the molecular connection, interacting with cellulose microfibrils and lignins, contributing to wood integrity (biological function) but also to recalcitrance (technical challenge). The dynamics of hemicelluloses in hydrated form and the molecular features that modulate interactions with other wood polymers are still controversial. The research program will decipher the molecular structure of wood hemicelluloses and their effect on the interaction with cellulose surfaces and lignin. The effect of hydration and the surrounding environments on the conformation and aggregation will be also investigated. Fundamental understanding on the hemicellulose role in plant cell walls is important in all facets of the WWSC, from wood disintegration, enzyme activity and solubility, to controlled chemical modification processes and technical properties in advanced materials. To resolve these fundamental questions on the structure and function of hemicelluloses, we will integrate advanced molecular characterization by mass spectrometry (MS) and nuclear magnetic resonance (NMR), molecular dynamic simulations, microscopy and scattering techniques.