By means of gel permeation chromatography analysis, the molecular weights and molecular weight distributions of liquefied wood obtained under various liquefaction conditions and species of catalysts were investigated in order to trace the change in the structural characteristics of the liquefied wood. The results indicated that during the liquefaction reaction, wood components were subjected to decomposition, phenolation, and recondensation. The intensities of these reactions depended greatly on the reaction conditions and the species of catalysts, and their competing result determined the structural characteristics of the resulting liquefied wood.