The effect of mechanical alloying on Zn-Sb alloy system is investigated with X-ray diffraction (XRD), laser grain size analysis and differential scanning calorimetry (DSC) respectively. The results of laser particle size analysis shows that the particle size decreases with increasing of the grinding time between 0 and 24 h. XRD and DSC results indicate that longer the grinding time of Zn-Sb is, the more content of Zn4Sb3 become in the product in this process.