In this study, Fe80B20 amorphous fibers with the diameter of 60 μm were prepared by the single roller melt-spinning method and annealed at 200°C, 300°C, 400°C, and 500°C, respectively. XRD results indicate that the fiber structure remains amorphous when the annealing temperature is below 400°C. α-Fe phase and Fe3B phase appear when the annealing temperature rises to 500°C, which is above the crystallization temperature of 449°C. The recrystallization activation energy is calculated to be 221 kJ/mol. The coercivity increases with increasing annealing temperature, which attributes to the increase of total anisotropy. All the as-spun and annealed fibers exhibit good resonance behavior for magnetostrictive sensors.