In this paper, we report the effect of thermal treatment at different temperatures (523, 623, and 723 K) on the magnetic properties of an amorphous powder with composition Fe72.5Si12.5B15 obtained by gas atomization. Differential scanning calorimetry curves indicate that a significant structural rearrangement takes place during annealing before crystallization. As expected, the intrinsic coercivity decreases with the annealing temperature, being the most significant drop from 3.26 to 0.44 Oe for the powder with a particle size <20 μm, non-annealed, and annealed at 723 K, respectively. An analysis of the effect of annealing on the anisotropy field distribution obtained directly from the magnetization curve is presented for both the non-annealed and the annealed sample with the lowest value of coercive field. The probability density function of the anisotropy field exhibits a lower applied field value at the maximum and is better fit by a Gaussian distribution after the heat treatment, which is a sign of better amorphicity after structural relaxation.