Dimensional stability is a key property of wood that significantly affects its applications. The effect of an ultrasound pretreatment on poplar wood (Populous tomentosa) dimensional stability was examined. During the pretreatments, wood samples were immersed in distilled water and treated ultrasonically under three different powers and frequencies. The samples were then analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The chemical transformation of the cell-wall material was studied and then associated with the change of water absorption and the swelling coefficient. The results showed that the water absorption decreased after the ultrasonic pretreatment. The axial and radial swelling coefficients of the pretreated samples decreased, while the tangential swelling coefficients increased. The volumetric swelling coefficient of pretreated specimens fluctuated near 4.48% (the volumetric swelling coefficient of untreated wood). Ultrasonic pretreatment increased the number of hydrophilic groups, such as the hydroxyl, acetyl, and uronic ester groups. Meanwhile, the pretreatment also increased the degree of crystallinity and reduced the available polar groups. These two factors together caused the change of the moisture absorption and the swelling coefficient of the pretreated wood. These conclusions suggest that the ultrasonic pretreatment is a promising method for further chemical modification of wood.