Using a special impulse device, the impulse electroless Ni-P alloy plating were prepared. The microstructure、crystallization and the starting activation energy for crystallization was investigated by TEM、XRD and DTA, compared with electroless Ni-P alloys plating. The results showed that the diffractive ring was wider when using impulse, depositing temperature dropped up to 65°C,and crystallization temperature rose up to 310°C. Furthermore , the starting activation energy for crystallization and crystallization temperature of impulse electroless Ni-P alloys plating measured were more than that of electroless plating in the heating rate at 5、10、20、 40K/min, and it was also higher in the amorphous disorder degree and the starting crystallization temperature. Impulse electroless Ni-P alloys plating had better performance of thermal stability.