Wood/methylolurea composite was prepared with the in-situ polymerization. The green timber with high moisture content was impregnated by a pulse-dipping machine and then was dried in a hot-press drying kiln. The cross-linking reaction was taken under the heat treatment between the wood modifier and the wood composition, including cellulose, hemicelluloses, and lignin. The chemical composition was analyzed according to the Chinese standard, including X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR) and energy dispersive analysis of X-rays (EDXA). The changes in chemical composition of modified wood and carbon and nitrogen element were disused in the research. The results showed that the content of water extraction and benzene alcohol extraction increased 187.43% and 230.87% respectively compared with the natural wood, while the lignin and holocellulose decreased 26.55% and 26.39% respectively. XPS showed that the concentrations of O and C atoms increased 9.4% and N element content increased 137.2%. 13C-NMR analysis showed that chemical reaction of the hydroxyl methyl urea with the hydroxyl in timber structure took place, with the reduction of hydroxyl content and increase in ether bond content. EDXA showed that the processing method can get impregnated modification wood and nitrogen element is evenly distributed in wood cell walls and intercellular space.