AbstractThe process of cooking with solid alkali is a novel and efficient technology. In the present work, milled wood lignin (MWL) and water-soluble milled wood lignin (WMWL) were used as the raw materials to research their properties when cooking with MgO and active oxygen. Before and after cooking, the lignin content of the samples was estimated using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), heteronuclear single-quantum coherence-nuclear magnetic resonance (HSQC-NMR), and gel permeation chromatography (GPC). The results showed that the properties of the MWL and WMWL were different. The G unit and A′structure in WMWL were more easily degraded than that in the MWL, where the G unit could be oxidized into a novel G′ unit. The D structure in the MWL with a weak signal could be thoroughly degraded, and the P structure was only present in WMWL and could be generated during the cooking process.