Abstract: The batch distillation experiments of bio-oil model compounds were carried out in a pilot rectification column. The distilled fractions of bio-oil model compounds at atmospheric pressure and vacuum distillation were compared by changing the vacuum degree in the system, and the variations of each component in the fractions were analyzed and summarized. The results show that the total distillate rate of bio-oil model compounds increases, the coking rate decreases, the moisture is more likely to be evaporated, the initial distillation temperature of organics in the fraction decreases, and the distillate rate increases with the rise in the vacuum degree of the system. Therefore, increasing the vacuum degrees can effectively separate the components of the bio-oil model compounds and reduce the energy loss. When the vacuum degree is −0.08 MPa, the distillation effect of the bio-oil model compounds is optimum. The distillate rate of acetic acid and furfural can reach 99.50% and 65.88%, respectively, and the distillate rates of phenol and guaiacol are both over 25%.