Abstract: The ordering of the α-Fe(Si) crystallization phase in annealed Fe73.5Cu1Mo3Si13.5B9 alloy has been studied using XRD method. The α-Fe(Si) phase in Fe73.5Cu1Mo3Si13.5B9 alloy annealed at 460℃ for 1 h consists of the DO3-type ordered region with spherical shape and disordered region. The size of DO3 ordered region increases with the annealing temperature. When the annealing temperature is 560℃, the size of the ordered region in the α-Fe(Si) grain is 14.0nm,which is nearly as large as that of the α-Fe(Si) grain (14.2 nm) and the degree of order of the α-Fe(Si) phase is about 0.78. When Fe73.5Cu1 Mo3Si13.5B9 amorphous alloy is annealed at 520℃, with the increment of the annealing time, the shape of the DO3 ordered region in the α-Fe(Si) phase is spheroidal at the beginning of the annealing and becomes spherical and has asize of 12.8 nm when the annealing time is 60 min. In addition, the DO3 superlattice lines of the α-Fe(Si) phase will vanish if Fe73.5Cu1Mo3Si13.5 B9 amorphous alloy is annealed for 1 h at 750℃.