Amorphous Ni-P alloys were prepared via electroless plating and annealing at 200°C at different times to obtain different microstructures. The effects of low-temperature annealing on the properties of amorphous Ni-P alloys were studied. The local atomic structure of the annealed amorphous Ni-P alloys was analyzed by calculating the atomic pair distribution function from their X-ray diffraction patterns. The results indicate that the properties of the annealed amorphous Ni-P alloys are closely related to the order atomic cluster size. However, these annealed Ni-P alloys maintained their amorphous structure at different annealing times. The variation in microhardness is in agreement with the change in cluster size. By contrast, the corrosion resistance of the annealed alloys in 3.5 wt% NaCl solution increases with the decrease in order cluster size.