A study has examined the effect of mixing methods on the thermal stability and detonation characteristics of ammonium nitrate (AN) and sodium chloride (NaCl) mixtures. NaCl was mixed with AN by two methods. The thermal stability, detonation velocity and structural properties were investigated by differential scanning calorimetry (DSC), measurement of detonation velocity and X-ray diffraction (XRD). For the mechanical mixing method, in all tested scope of proportions of NaCl in the mixtures, activation energies increase when the proportion of NaCl increases; for solution mixing method, the activation energies decrease first and then start to increase as the proportion of NaCl increases. The detonation velocity of AN-NaCl mixtures prepared by two mixing methods also showed different results. The results indicate that the mixing methods significantly affect the thermal stability and detonation characteristics of AN.