AbstractTo achieve high value-added utilization of lignin extracted from the biorefinery process in the wood composite industry, binderless particle boards were manufactured by bamboo materials combined with alkaline lignin (AL) in various proportions under various hot-pressing conditions. To elucidate the reactivity and chemical transformations of lignin macromolecules during the hot-pressing process, lignin samples were isolated from the corresponding boards and characterized by high-performance anion-exchange chromatography (HPAEC), gel permeation chromatography (GPC), quantitative 31P-NMR, and 2D-HSQC NMR. The best bonding strength (1.36 MPa) of the binderless particle boards was obtained under the conditions of 180 °C, pressure 5 MPa, and lignin/bamboo mass ratio 0.4. The molecular weight of the lignin samples decreased from 3260 to 1420 g/mol during hot-pressing. The NMR results showed that the contents of β-O-4' and β-β' linkages were reduced and β-5' linkages were increased as the hot-pressing temperature rose. Simultaneously, the percentage of G-type and H-type lignins as well as the content of phenolic OH increased.