ZnO powder showed anomalous evaporation behavior after its mechanical milling treatment under high-energy conditions. The amount of generated vapor is about 10 times higher in the first 15 min of annealing at 1300 °C than that of unmilled ZnO powders. The strong ball impacts are responsible for the greatly enhanced evaporation ability. Low-energy ball milling involving shearing actions and rare weak impacts leads only to a small evaporation rate enhancement. The possible explanation of the high evaporation rate of the heavily milled material is the existence of large fraction of weakly bonded atoms in grain boundaries, surface defects and strained areas.