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Activated carbon fibers were prepared from liquefied wood through stream activation. The effects of activation temperature and time on the microstructure and surface functional groups of the liquefied wood activated carbon fibers (LWACFs) were studied using analysis of burning behavior, X-ray diffraction, nitrogen adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and SEM. The results showed that the burn-off value of the LWACFs increased gradually with the increase in temperature or time. All the LWACFs were far from being structurally graphitized, and in general, as temperature or time increased, the degree of graphitization and thickness of crystal structure increased. In addition, the LWACFs possessed rich micropores, and their specific surface area, pore volume, micropore size, and mesopore quantity were directly related to the activation temperature or time. The maximum specific surface area was found to be 2641 m2/g. The fractal dimension values of all samples were close to 3, indicating that their surfaces were very rough. Furthermore, with an increase in temperature or time, the elemental content of carbon increased, while that of oxygen decreased. Meanwhile, as the temperature or time increased, the relative content of graphitic carbon decreased, whereas that of carbon bonded to oxygen-containing functions increased. The surface of samples prepared at higher temperature or with longer time formed a considerable amount of holes.