ZrO2 nano-powders were prepared by a microemulsion process with the water-in-oil system of water/cyclohexane/Triton X-100/hexyl alcohol. The influence of cosurfactant content and the heterogeneous distillation process on the structure and properties of the particles was studied. XRD analysis showed that the cosurfactant content has little influence on the crystal phase of ZrO2. With the increasing mass ratio of cosurfactant to surfactant from 0.3 to 0.5 and 0.7, the average size of ZrO2 powders increases from 23.3 to 25.2 and 27.5 nm. The heterogeneous distillation process can effectively inhibit the formation of hard agglomeration during evaporation and increase the specific surface areas of ZrO2 powders.