By means of X ray and gas chromatography analysis, the crystalline structure of untreated wood , alkali treated wood and benzylated wood and their liquefaction in toluene and tetrahydrofufan with HCl as a catalyst were studied .The upper solution of benzylated wood was also studied by GC MS analysis. It proved that the introduction of bulky benzyl group in wood significantly changed the crystalline structure of wood ,enlarging the free volume which facilitated the penetration of solvent into the matrix of treated wood, thus tremendously enhancing thesolubility in solvent,compared to untreated wood and alkali treated wood. The percentage of residue decreased and the combined solvent increased with the increase of weight gain revealed that the liquefaction process became easy. Furthermore, the factors that influenced the liquefaction of benzylated wood were investigated. It showed that the liquefaction performance was improved with the increase of liquefaction time and the amount of catalyst when toluene was used as a solvent, especially in the presence of THF as solvent, there existed the optimum liquefaction time and the amount of catalyst .