The proposed research aims at obtaining atomic-level information to construct four structural models that reflect the supramolecular architecture of plant secondary cell walls in hardwoods and softwoods, and before and after fungal degradation. Such information will fill a long-standing gap between the microbe-regulated energy-relevant bioprocess and the molecular structure of biomolecules. Since the biomass-degrading microbes produce various enzymes for digesting lignin and degrading polysaccharides into metabolizable sugars, a molecular level understanding of this fungi-plant complex has the potential to substantially advance our fundamental knowledge of global carbon cycles and facilitate biofuel production and biomaterial development. To achieve these goals, we will need a systematic investigation of the structure, dynamics and hydration of biomolecules, for example, complex carbohydrates, proteins and lignin, in wood cell walls. Typically, these macromolecules are highly polymorphic in structure, insoluble, and non-crystalline, thus evading high-resolution characterization. Recently, we have employed multidimensional solid-state Nuclear Magnetic Resonance (NMR) spectroscopy to investigate the cell wall structure of fungi and grasses in their native state and in whole cells, without any need for sample processing or treatment. Two studies have already been published on Nature Communications, which provide the structural and methodology basis for investigating other plant and microbial systems. Here we will use our established expertise to investigate woods and their degrading, white-rot fungi. As the PI's current facility lacks high-field magnet, the proposed work will require frequent access to the state-of-art NMR facility at EMSL, especially the 850 MHz spectrometer, which will provide the resolution needed for characterizing these complex biosystems. Meanwhile, the NMR team at EMSL has extensive experience in plant research and collaborations with the leading scientists will substantially benefit the progress of the project.