Lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear C-13-C-13 correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.