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W17.9Ni65.6B13.5V3(at. %)amorphous alloy was prepared by melt spinning method. X-ray diffraction pattern and differential scanning calorimeter were applied to investigate non-isothermal crystallization kinetics of the amorphous alloy. As the heating rate was increased, the values of the glass transition temperature, the initial crystallization temperature and the peak temperature were gone up, suggesting that the amorphous alloy had obvious crystallization kinetics. The crystallization activation energy of W17.9Ni65.6B13.5V3 amorphous alloy calculated by Kissinger equations and Ozawa equations was 456.9kJ/mol and 471.1kJ/mol, respectively, indicating that the amorphous alloy possessed high thermal stability. The values of crystallization activation energy Ex were smaller than nucleation activation energy Ep calculated by Kissinger equation and Ozawa equation at the characteristics of the temperature, which showed that nucleation process more easily than the grain growth process, indicating that ultrafine grains structure could be easily obtained at certain conditions.