The short‐range structure of annealed amorphous FeBSiCuNb alloys is investigated by means of X‐ray diffraction. At temperatures higher than 450 °C b.c.c. Fe(Si) is formed in an amorphous matrix. The crystallization is accompanied by a change of the local symmetry of Fe atom environment. The short‐range order of the formed crystalline Fe(Si) phase is not realized in the amorphous as‐quenched state. Due to the precipitation of iron and silicon during crystallization the chemical composition and the short‐range order of the amorphous matrix are changed.