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Corn stalk is one of the most abundant agricultural residues in China. In this experiment, corn stalks were hot-pressed to prepare formalin-free particleboard. Milled wood lignin (MWL) samples were isolated from original and hot-pressed corn stalks. To illuminate the self-bonding mechanism of binderless particleboard, the structural characteristics of original corn stalk, hot-pressed corn stalk, and MWL samples were thoroughly investigated by Fourier transform infrared spectroscopy (FT-IR), solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy (CP-MAS 13 C-NMR), X-ray diffraction (XRD), carbon-13 nuclear magnetic resonance spectroscopy ( 13 C-NMR) and gel permeation chromatography(GPC). The degradation of hemicellulose and a portion of amorphous cellulose occurred during hot-pressing. Hot-pressing increased the crystallinity and crystallite size of cellulose in treated corn stalk. The analysis of MWL showed that hotpressing resulted in corn stalk lignin depolymerization through cleavage of a substantial portion of the β-O-4 linkages in lignin, as well as the decrease of molecular weight of lignin in corn stalk. In addition, acidcatalyzed condensation occurred between lignin and xylose when liberated from hemicellulose. These results demonstrated that condensation between lignin and xylose may contribute to the selfbonding mechanism and improve board properties.