In this work, willow fiber was extracted from willow inner bark and modified with alkali solution of various concentrations, temperature and time. The morphology, surface functional group, crystal and thermal stability were investigated by using a scanning electron microscopy, a Fourier transform infrared spectroscopy, an X-ray powder diffractometer, and a simultaneous thermal analyzer, respectively. The acid (H2SO4, 2 ml/l) extraction procedure removed the hemicellulose and part of lignin from willow bark, cleared the aggregation of WB, kept the crystal structure of willow fiber, dramatically increased the crystal length of fiber (from 18.46 to 30.15 nm), and enhanced the onset degradation temperature (from 262.23℃ to 297.62℃) and chemical reactivity (DTG: from 0.57%/s to 0.84%/s). The alkali treatment further removed lignin from willow fiber, smoothed the fiber surface, increased the intensity of cellulose [Formula: see text] from 646 counts to 1292 counts, and lengthened the crystal length from 30.15 to 41.84 nm. Varying the alkali treating condition, the crystal index and thermal stability reached to the climax at 60℃ of treating temperature and 7 h treating time. The treated willow fiber may have potential applications to composite with polymer, and to be used in pharmaceutical field as additives.